RU2109762C1 - Method of producing petroleum polymeric resin - Google Patents

Abstract

FIELD: chemical industry, more particularly production of para, paint materials, and rubbers. SUBSTANCE: present invention describes method for producing petroleum polymeric resin by polymerization of unsaturated compounds of polycondensate fractions at 30-130 in the presence of 1-4 wt % of mixture of diethylaluminium chloride and production waste resulting from microspherical polypropylene polymerization catalyst at weight ratio of (0.1-10.0): 1.0, respectively. Production waste represents mixture comprising, wt.- %: titanium chloride-aluminium chloride, 15; diisoamyl ether, 21; and heptene, 54. EFFECT: more efficient production method. 3 tbl

Description

 The invention relates to a method for producing petroleum polymer resins (NPS) - substitutes for expensive and scarce products of natural origin: vegetable oils (in paints and varnishes), rosin (in paper production), as well as wood-pyrogenic and indene-coumarone resins (in rubber compounds and production rubber products).

Known methods for producing NPS from pyrocondensate fractions by ionic and radical polymerization. The disadvantage of the method of radical polymerization is the need to carry out the process under harsh conditions: 250 ^o C, 11.5 atm, 3.5 hours (thermal polymerization), or a longer reaction time: 15 hours at 160 ^o C (polymerization initiated by isopropylbenzene hydroperoxide).

 Closest to the proposed is the method of ionic polymerization under the action of aluminum chloride and its complexes. The polymerization in this case proceeds under milder conditions, but also has disadvantages. The disadvantages of this method are the difficulties of working with dry aluminum chloride: it is difficult to dose; impossible to use in a continuous process; it is easily hydrolyzed, as a result of which its catalytic activity decreases and lumps form.

 The aim of the invention is to eliminate these disadvantages. This goal is achieved through the use of unsaturated compounds of diethylaluminium chloride pyro-condensate fractions (DEAC) as a catalyst for the polymerization process and waste products from the production of microspherical propylene polymerization catalyst in a mass ratio (0.1 - 10.0): 1.

 Using this catalyst allows you to: eliminate the difficulties of working with aluminum chloride; eliminate the stage of destruction of microspherical catalyst waste, which consists in neutralizing the products of washing the microspherical catalyst with subsequent distillation of heptane and burning it; improve the environmental situation in the workplace.

Wastes from the production of the microspherical catalyst are a mixture of the following composition,%: TiCl ₄ - 15; AlCl ₃ - 10; diisoamyl ether -21; heptane - 54.

Example (example 2, table 1). 2425 kg of pyrocondensate fractions with boiling limits of 130 - 190 ^o C are loaded into the reactor with an anchor mixer. At a temperature of 35 - 40 ^o C, with the mixer working, 250 kg of production waste are fed into the reactor (titanium tetrachloride content TiCl ₄ - rel. equals 37.5 kg), then the temperature is increased to 40 - 50 ^o C and serves 37.5 kg DEAC for 0.5 hours (ratio of TiCl ₄ - rel.: DEAC = 1: 1). The total amount of catalyst is 3% of the weight of the pyrocondensate fractions. After that, the temperature was raised to 70 ^° C. and the reaction mixture was stirred for 3 hours. Then 120 kg of a 40% aqueous solution of NaOH are charged into the reactor and stirred for one hour at 95-100 ^° C. The reactor is then cooled and after 24 hours the aqueous layer containing NaCl and titanium and aluminum hydroxides is separated from the bottom of the reactor. Then steam is supplied to the reactor, the reactor is heated to 150 ^° C. and the azeotrope of the solvents is distilled off with water. Resin yield was 49%, the softening temperature of 84 ^o C, a color of 100 mg I _2/100 ml, an acid number of 0.8 mg KOH / 1 g, iodine number 46.4 g I _2/100 g

 The following examples confirming the influence of reaction conditions on the quality of the resin obtained by polymerization of unsaturated compounds of the pyrocondensate fractions are presented in tables 1-3.

Thus, as can be seen from the examples presented, the use of diethylaluminium chloride and the production of microspherical catalyst as a catalyst for the polymerization of unsaturated compounds of pyrocondensate fractions makes it possible to obtain NPS with a yield of 14.2 - 51.2%, softening point 49 - 88 ^o C, color 60 - 400 mg I _2/100 ml, acid value of 0.4 - 2.4 mg KOH / 1 g, an iodine value of 39.1 - 59.8 g I _2/100 g at this optimal reaction conditions are as follows: ratio of TiCl ₄ - waste: DEAC = 1: (0.1 - 10.0); the amount of catalyst 1 to 4 wt.%; reaction temperature 30 - 130 ^o C.

The proposed method allows to simplify the technology of the polymerization process by eliminating the difficulties of working with AlCl ₃ ; eliminate the stage of destruction of microspherical catalyst waste and use cheap waste.

Claims (1)

A method of producing petroleum polymer resins by catalytic polymerization of unsaturated compounds of pyrocondensate fractions, characterized in that the polymerization is carried out at 30 - 130 ^o C in the presence of 1 to 4 wt.% A mixture of diethylaluminium chloride and waste products from the production of microspherical polypropylene polymerization catalyst in a mass ratio of 0.1 to 10, 0: 1.0, respectively, while production waste is a mixture of the following composition, wt.%:
Titanium tetrachloride - 15
Aluminum Chloride - 10
Diisoamyl ether - 21
Heptane - 54t

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