CS200055B1

CS200055B1 - Process for alkylating hydroxyarones with low molecular weight polymers or copolymers derived from o (-olefins)

Info

Publication number: CS200055B1
Application number: CS310778A
Authority: CS
Inventors: Jiri Pac; Jiri Sedlar; Ema Svejdova; Milos Uhlir; Jan Holcik; Milan Karvas; Mikulas Collak; Miroslav Magura
Original assignee: Jiri Pac; Jiri Sedlar; Ema Svejdova; Milos Uhlir; Jan Holcik; Milan Karvas; Mikulas Collak; Miroslav Magura
Priority date: 1978-05-15
Filing date: 1978-05-15
Publication date: 1980-08-29

Abstract

Vynález zdokonaluje alkylaoi hydroxyaronů nízkomolekulárníml polymery nebo kopolymery odvozenými od alfa-olofinů. Produkt alkyláce katalyzované bělicí hlinkou napojenou polyfosforoěnými kyselinami jo žlutý až hnědý. Zbarvení produktu zabrání 1 až 30 hmotnostních % práškového kovu, hořčíku, hliníku nebo zinkuvztaženo na hmotnost použitého katalyzátoru. Práškový kov se přidává do reakční směsi 'před počátkem alkylaoe.The invention improves the alkylation of hydroxyarones with low molecular weight polymers or copolymers derived from alpha-olefins. The product of the alkylation catalyzed by bleaching clay coupled with polyphosphoric acids is yellow to brown. The coloration of the product is prevented by 1 to 30% by weight of powdered metal, magnesium, aluminum or zinc, based on the weight of the catalyst used. The powdered metal is added to the reaction mixture before the alkylation begins.

Description

The invention relates to the alkylation of hydroxyarenes with oligomers of olefin olefins catalysed by bleaching earth linked with polyphosphoric acids.

Alkylation of hydroxyarenes by oligomers derived from di-olefins and from 2 to 4 carbon atoms, catalysed by various catalysts, in particular by bleaching clay bound with pyrophosphoric acid and tetrafeophoric acid, is described in CSO 174,677 and CSO 174,679.

The alkyls provide high molecular weight alkylsubstituted hydroxyarenes useful as stabilizers for polymers, especially polyolefins, or as motor fuel and oil enhancers.

In CSA 182 585, a favorable cecatalytic effect of 5-15% by weight of water contained in the catalytic system on the yield of the alkylation roacoo was described. The alkylated hydroxyarenes obtained in this process are, however, tinted with small amounts of compounds, resulting in any of the oxidation-census-type side reactions, so that the color of the product is yellow to brown. This coloring can be removed by the clay purification by bleaching with clay, but during storage the color shade of the product has become deeper again.

It has now been found that the disadvantage of said process can be overcome by the addition of metal powders 11 and III. a perlodlocyl group to an alkylation mixture.

The present invention is a method alkylaoe hydroxyarenů low molecular weight polymers and copolymers derived from olefins having 2 to 4 carbon atoms and the medium by a numerical grade pelymeračním 5-50, clay catalyzed bělioí connected polyfosforočnými acids village naked vseroe ^H (y ₊ 2) ^R ° (3n + 1) ^{wherein the} average n is 2 to 6, in an amount of 5 to 35% by weight of bleached clay containing 5 to 15% by weight of water, based on the weight of the catalyst, and 1 to 30% by weight of powdered magnesium, aluminum or zinc, also on the weight of catalyst used.

The metal powders 00 are dosed into the syetam before the start of the alkylae. The optimum size of the metal part is in the range of 10 to 300 depending on the heater of the metal used. The addition of the metal threshold substantially reduces the formation of by-products of color, and therefore the prepared alkyllevel hydro-avones are only slightly colored in zoole. The degree of coloration is determined by comparison with standard scale standards according to Oardnor (ASTM D 154-47).

The following non-limiting examples illustrate the invention.

All parts and materials in the examples are by weight unless otherwise specified. The results are summarized in Table I.

Example 1

200 parts of polypropylene oloyl of molecular weight 480 l and 550 (cryosclock determination) were added to the grate at a temperature of 60 ° C with 50 parts of 2,6-xyloaol of 200 diloohol of toluene. To this solution was suspended a slurry of 10 parts of powdered aluminum (size about 15yun) in 50 parts of polypropylene oil and 44 parts of an alkylaine catalyst consisting of 30 parts of white clay and 10 parts of polyphosphoric acid containing 81.5% phosphorous pentoxide and 4 parts of water . Water was added to the bleached clay, polyphosphoric acid-linked, in the form of steam, and the amount of defect added was monitored by weight gain. For 7.5 hours, the roots of the mixture were heated to reflux, the catalyst together with the pulverulent metal was filtered off from the filtrate by distilling off toluene together with the unreacted 2,6-xylonol.

Analysis showed that the final product contained 7.9% 2,6-xylonol bound, which at a given molecular weight was about 40% of the alkyl-bound product content.

The degree of coloring of the thus prepared alkylated 2,6-xylonol corresponds to otalene 8. 2 standard comparisons according to Oardnor, while alkyla without the addition of powdered metal yielded a product whose coloring was consistent with the taring »6. 9 ·

Example 2

A solution of 27 parts of freshly distilled o-crosol, 125 parts of propylone oligosor (intermediate polymorph 16) and 112 parts of xylene was charged with 24 parts of catalyst (prepared from 15 parts bleaching earth * moistened with 1 part water). containing 82 .mu.l of phosphorus pentoxide) and 6 parts of powdered zinc (20 to 40 .mu.m in bulk).

The roasting mixture was stirred and held at 140 ° C for 8 hours after filtering off the catalyst, de-distilling the solvent, and treating the treated o-cresol with a pale yellow, viscous liquid containing 7.6% of the o-crosol bound in the product.

Coloring level according to Gardnor scale 3.

The product prepared according to the same procedure, but with the addition of metal, had a degree of coloring of 10.

Example 3% solution of alkylated 2,6-xylenol in propylene oligomer, characterized by a dynamic viscosity at 20 ° C, (1.10 ³ m / s), a light weight (0.86 g.cra ^-3 ), a pour point (- 14 + 3 ° 0) * tupnia color according to Gardner 2, hyl obtained following i

To the alkylation mixture, composed of 38 kg of 2,6-xylenel, 125 kg of propylene oligemers (medium polymorphic otupene 12), 112 kg of xylene and 24 kg of catalyst treated with 900 ml of water * was added 5 kg of powdered magnesium (200 µm particle size) . After alkylation (8 hours > 135-138 ° C) and filtering off the pulverulent metal and catalyst, the solvent and unreacted 2,6-xylenol were removed under reduced pressure of 1.6 kPa at 150-160 ° C.

Parallel alkylation using a pulverulent metal yielded a product whose coloring was comparable to standard # 9 of Gardner's standard comparative color shade.

Table 1i Effect of the addition of powdered metals to the alkylation mixture on the reduction in color of the resulting alkylated hydroxyarenes

Alkylaoe by

Claims

Method of alkylation hydroxyarenů nískomolekulárními polymers or copolymers derived from the FLC-olefins with two to four carbon atoms and the medium by a numerical polymerization degree of 10 to 20 linked clay catalyzed by Bull pelyfoeferečnýml vsoroe acids of ^H (n + 2) ^R ° (3n + 1) ^{wherein the} ^{composition is} from 5 to 35% by weight of the bleached earth containing from 5 to 15% by weight of water, based on the catalyst haotnoate, characterized in that they add to the reaction mixture cross-magnesium, zinc or aluminum in an amount of 1 to 30% by weight, based on the weight of the catalyst.