RU2086569C1 - Method for production of petroleum polymer resins - Google Patents

Abstract

FIELD: production of petroleum polymer resins. SUBSTANCE: resins are prepared by polymerization of unsaturated compounds of fractions of liquid products of pyrolysis. The process is carried out at 30-130 C in the presence of aluminium powder and waste of production of microspherical catalyst of polymerization of propylene, weight ratio of Al:TICl₄ being (0.02-0.2): 1.0. Concentration of catalyst is 1-4 wt.-%. Waste comprises mixture which contains, wt. -%: titanium tetrachloride, 15; aluminium chloride, 10; diisoamyl ether, 21; and heptane, 54. EFFECT: improved efficiency. 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 disadvantages of the method of radical polymerization are the necessity of carrying out the process under severe 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. Known methods for the polymerization of various unsaturated fractions of pyrocondensate under the action of aluminum chloride and its complexes at 60 ^o C. Known methods for the polymerization of fractions of hydrocarbons With ₄ -C ₅ formed during the pyrolysis of oil in the presence of a 20% solution of Al ₂ (C ₂ H ₅ ) ₃ Cl ₃ in an aliphatic hydrocarbon at a temperature of 15 ^o C. Ionic polymerization proceeds under milder conditions, but also has disadvantages. In the case of using aluminum chloride, the disadvantages include difficulties in working with dry aluminum chloride, its high hygroscopicity, the inability to use in a continuous process, and the difficulty of dosing. When using organoaluminum catalysts, the disadvantages include their high cost, high fire and explosion hazard.

 The aim of the invention is to simplify the technology for the production of NPS, eliminate the noted disadvantages and reduce the cost of the polymerization product.

 The goal is achieved through the use of aluminum powder as the polymerization catalyst and the production waste of the microspherical polymerization of propylene (titanium trichloride) in a weight ratio (0.02-0.2): 1.0.

The waste from the production of the catalyst, the mother liquor after washing the titanium trichloride, contains: TiCl ₄ 15% AlCl ₃ 10% diisoamyl ether - 21% heptane 54%
Using the proposed catalytic system allows you to: eliminate the difficulties of working with aluminum chloride; avoid the use of expensive, fire, explosive organoaluminum catalysts; eliminate the stage of destruction of the production of microspherical catalyst, which consists in neutralizing the washing products of TiCl ₃ with subsequent distillation and combustion of heptane; improve the environmental situation in the workplace; reduce the cost of resin through the use of production waste.

Example (example 2, table 2). 2425 kg of pyrocondensate fractions with a boiling range of 130-190 ^o C are loaded into the reactor with an anchor mixer. At a temperature of 35-40 ^o C, with a working stirrer, 12.5 kg of aluminum powder and 416.6 kg of microspherical catalyst waste containing 15 are loaded into the reactor % TiCl ₄ , i.e. 62.5 kg. The content of the catalytic complex by weight of the pyrocondensate fraction is 3%; the ratio between the components of the Al: TiCl ₄ complex is 0.2: 1.0. After loading the catalytic complex, the reaction temperature was raised to 70 ^° C and the reaction was carried out for 4 hours. At the end of this time, 100 kg of a 40% aqueous NaOH solution was fed into the reactor and the reaction mixture was stirred for 1 hour. After that, the reactor was cooled and An aqueous layer containing NaCl, titanium and aluminum hydroxides is lowered from the bottom of the reactor for 24 hours. From the working volume of the reactor at a temperature of 150-160 ^o C with water vapor, the solvent is distilled off. Resin yield was 44% softening temperature of 68 ^o C, the color of 60 mg I _2/100 ml, an acid number of 0.9 mg KOH / 1 g, an iodine value of 52.7 g I _2/100 g

Examples confirming the influence of the polymerization conditions of various fractions of the pyrolysis products: catalyst concentration, reaction temperature, the ratio of the amount of aluminum powder and the waste products of the production of microspherical catalyst (TiCl ₄ -ex) on the quality of the obtained resin are presented in table. 1-3.

Thus, use as a polymerization catalyst Al-powder and microspheroidal catalyst production waste polymerization of propylene produces PS with a softening point 46-78 ^o C, the color of 20-80 mg I _2/100 ml, acid value of 0,4-3,2 mg KOH / g 1, an iodine number of 48,1-58,3 g I _2/100 g yield 20,5-48,0.

Claims (1)

A method of producing petroleum polymer resins by catalytic polymerization of fractions of pyrolysis products, characterized in that the polymerization is carried out at 30 130 ^o In the presence of 1 to 4 wt. a catalyst consisting of aluminum powder and waste production of a microspherical catalyst for the polymerization of propylene at a mass ratio of 0.02 0.2 1.0, respectively, production waste is a mixture of the following composition, wt. Titanium tetrachloride 15
Aluminum Chloride 10
Diisoamyl ether 21
Heptane 54a

Images