Process for the production of 2,5-dimethyl-2,5-di-t-butylperoxy-

Details Process for the production of 2,5-dimethyl-2,5-di-t-butylperoxy- Process for the production of 2,5-dimethyl-2,5-di-t-butylperoxy-

1998-10-12

2000-03-07

Geist, Gary

Organic compounds -- part of the class 532-570 series

Organic compounds

Oxygen containing

568558, C07C40904

Patent

active

060342803

DESCRIPTION:

BRIEF SUMMARY
DESCRIPTION

The invention concerns a process for the production of 2,5-dimethyl-2,5-di-t-butylperoxy-hexane starting from 2,5 dimethyl-1,5-hexadiene and t-butylhydroperoxide.
2,5-dimethyl-2,5-di-t-butylperoxy-hexane (DHBP) is an important peroxide for cross-linking elastomers and thermoplastics and for the selective degradation of high molecular polypropylene.
The usual production process for DHBP starts with 2,5dimethyl-hexane-2,5-diol. This is reacted with hydrogen peroxide in a strong acidic medium to form the dihydroperoxide. The excess hydrogen peroxide is removed by suitable washing steps and the dihydroperoxide is further reacted with t-butanol also in a strong acidic medium to form DHBP.
The disadvantages of this two-step process are the poor yields (60-65% relative to the diol used), the long process times, the handling of the solid dihydroperoxide (critical compound with regard to safety) and the formation of large amounts of acidic liquid waste and wash solutions.
2,5-Dimethyl-hexane-2,5-diol cannot be reacted with t-butylhydroperoxide (TBHP) in acidic medium since the diol is very readily cyclysed to the 2,2,5,5-tetra-methyltetrahydrofuran under the influence of acid.
The reaction of 2,5-dimethyl-1,5-hexadiene with TBHP using an acid catalyst is described in FR-PS 1 291 965. Perchloric acid, sulfuric acid, hydrogen chloride gas, toluenesulfonic acid and similar strong acids are listed as suitable acids. It is also mentioned that it is preferable to work in an anhydrous medium but 75% technical TBHP is also used in the examples. However, the reaction of 2,5-dimethyl-1,5-hexadiene with 75% TBHP and p-toluenesulfonic acid only results in a yield of 26% of DHBP. But even under anhydrous conditions high yields cannot be achieved with these stated acids. Furthermore the TBHP used in the FR-PS examples with a percentage of 98-99% is an extremely dangerous substance which can be neither produced nor handled on a technical scale. In addition large amounts of undesired by-products are formed in the reaction which can only be removed by distillative purification. This is an unacceptable process on an industrial scale for safety reasons.
There is therefore a need for a process which allows DHBP to be produced safely and environmentally-friendly with good yields and in short process cycles. The object of the invention was therefore to satisfy this need.
Surprisingly it was now found, and this is the basis of the invention, that in the presence of Lewis acids in a substantially anhydrous medium, DHBP can be obtained from 2,5-dimethyl-1,5-hexadiene and TBHP in short reaction times and in good yields and in satisfactory product quality.
The object defined above is therefore achieved according to the invention by a process for the production of 2,5-dimethyl-2,5-di-t-butylperoxy-hexane by reacting 2,5dimethyl-1,5-hexadiene with t-butylhydroperoxide under acid catalysis which is characterized in that the reaction is carried out in the presence of an electron pair acceptor Lewis acid in a substantially anhydrous solvent.
A major advantage of the invention from a safety standpoint is that anhydrous and thus hazardous TBHP does not have to be used, but rather that the water can be separated from the mixture of technical water-containing TBHP and 2,5-dimethyl-1,5-hexadiene by addition of relatively small amounts of dilute sulfuric acid or calcium chloride. The reaction to form DHBP then takes place after addition of the Lewis acid catalyst.
Suitable Lewis acids that can among others be used are:
Boron trifluoride etherate, zinc chloride ether complexes, anhydrous complexes of sulfuric acid with boric acid, phosphotungstic acid or lithium perchlorate or magnesium perchlorate in organic solvents such as e.g. ether.
The reaction is preferably carried out at a temperature of -10.degree. C. to +50.degree. C. and in particular in the range of 0.degree. C. to 30.degree. C.
TBHP can be used in a highly concentrated form. However, technical water-containing TBHP at a 60 to 80% concentration is preferred. TBHP is preferably u

REFERENCES:
patent: 3086966 (1963-04-01), Mageli
patent: 3135805 (1964-06-01), Gilmont
patent: 5210320 (1993-05-01), Tso
patent: 5371298 (1994-12-01), Pourreau
CA:73109099 abs of Tetrahedron by Kashiwagi 26 (15) pp. 3631-7 1970.
CA:106:42843 abs of J Organomet Chem. by Heidrich 312 (3) pp. 329-33 1986.
Cotton and Wilkinson "Advanced Inorganic Chemistry" textbook pp. 233-235 1972.

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