RU2356914C1 - Method of obtaining polymeric petroleum resin - Google Patents

Abstract

FIELD: chemistry.

SUBSTANCE: present invention relates to the technology of producing polymeric petroleum resin. Description is given of a method of obtaining polymeric petroleum resin through cation cooligomerisation of unsaturated hydrocarbons consisting of liquid secondary fractions of pyrolysis and their block-cooligomerisation with an oily product of thermostatting the initial fraction in the presence of a catalytic complex of aluminium chloride and a promoter of olefin oxide at high temperature, with subsequent deactivation of the catalytic complex with a base and distillation of unreacted hydrocarbons. The method is distinguished by that, the catalyst deactivator used is a mixture of Lewis bases, wt %: 20.0-50.0 olefin oxide, 50.0-80.0 C₄-C₅ alcohol, 0.1-0.7 C₄-C₁₃ carbonyl compounds and 0.01-0.15 water at molar ratios oxide : alcohol : carbonyl compounds : water : aluminium chloride equal to 4.90-5.00 : 3.90-8.00 : 0.01-0.05 : 0.01-0.05 : 1.00. These bases are gradually added to the block-cooligomerisation mixture at high temperature.

EFFECT: higher output and adhesion of polymeric petroleum resin, lower bromine number of the polymeric petroleum resin, increased environmental safety of the process and simplification of technology.

3 cl, 1 tbl, 5 ex

Description

The invention relates to a technology for the production of oil-polymer resins (NPS) by cationic co-oligomerization of unsaturated hydrocarbons in the liquid fractions of the pyrolysis of petroleum products (WFP) and block oligomerization with the oily product of their preliminary thermo-oligomerization.

NPS with a softening temperature exceeding 60 ° C are used in the manufacture of paints, varnishes, construction materials, construction materials, paper, glues, adhesives and other products [E.M. Varshaver et al. // Chemistry and technology of fuels and oils, 1979, No. 3, p. 7].

The technical and economic characteristics of production and consumer properties of NPS obtained by cationic (using mainly anhydrous aluminum chloride complexes with a promoter as a catalyst) co-oligomerization are higher than thermal or free radical ones [S.M. Aliev et al. Preparation and application synthetic paints and varnishes. (Analytical review). CIONT, PIC VINITI, N 25. Baku 1983], therefore, in industrialized countries, mainly cationic NPS (KNPS) are produced [A.D. Berents et al. Processing of liquid pyrolysis products. - M. Chemistry, 1985].

A known method for the production of KNPS by block oligomerization of unsaturated hydrocarbons and their thermo-oligomer in the composition of the ZHFN in the presence of a complex of aluminum chloride with olefin oxide and its isomer at a temperature of 30-50 ° C, followed by deactivation of the catalyst with a base and distillation of unreacted hydrocarbons from a deactivate. The yield of KNPS is 75-95% of the mass of monomers (vinyltoluene, (methyl-) styrenes, (methyl-) indenes, divinylbenzenes; dimers of (methyl-) cyclopentadiene and its co-isomers with isoprene and p (DiCPD), conjugated dienes and (cyclo-) olefins with a double bond at the tertiary carbon atom), as well as their thermo-oligomers; softening temperature of about 118 ° C, color 80-120 units. IMSh [Application of Japan N55-80415, cl. C08F 249/00, 1980].

The disadvantage of this method is the low yield of KNPS.

The closest in technical essence to the claimed invention is a method for producing KNPS by co-oligomerization of unsaturated hydrocarbons in the composition of carefully purified and dried С ₉ -С ₁₀ -fractions of pyrolysis of oil products and block-oligomerization with an oily product (their preliminary co-oligomerization at 180-300 ° С, mainly 200-280 ° C, for 0.2-10, mainly 1-8 hours) in the presence of 0.5-5.0 wt.% The Friedel-Crafts acid complex (mainly 0.8-2.2% of the aluminum chloride complex) and propylene oxide promoter in molar the ratio of AlCl ₃ : propylene oxide, equal to 1.3-1.4: 1. The catalytic complex is introduced into the reaction mixture in the form of a solution in an aromatic hydrocarbon at a reactor temperature of preferably 30-60 ° C. and its contents are stirred for 1-6 hours. Then the catalyst is deactivated with 30% aqueous alkali, the deactivate is washed with water until neutral and the unreacted hydrocarbons are distilled off at a temperature of 180-190 ° C in a stream of nitrogen. The yield of KNPS is 62.9-91.4% of the mass of unsaturated hydrocarbons contained in the fraction or 32.8-48.0% of the mass of their mixture with alkylbenzenes and (alkyl-) polynuclear aromatic hydrocarbons.

Received KNPS is characterized by a softening temperature of 50-30 ° C, a color of 8-10 units. according to Gardner, 10-20 units. on an iodometric scale (mg J ₂ per 100 ml of an aqueous KJ solution), bromine number 26-50 (g Br ₂ per 100 g of resin), fully compatible with vegetable oil and alkyd resin [US Patent No. 4283518, cl. C08F 212/06 212/08, 08/11/1981].

The disadvantages of the method are the complexity and environmental hazard of the technology, dumping 5.3-8.1 tons of chemically contaminated waste water per 1 ton of KNPS, low yield, weather resistance, adhesion to solid surfaces and product elasticity. The task of the invention is to simplify, improve the environmental safety of technology and quality of KNPS, as well as increase output.

The problem is solved in that a mixture of Lewis bases, wt.%: 20.0-50.0 olefin oxide, 50.0-80.0 alcohol C ₄ -C ₅ , 0.1-0.7 is used as a catalyst deactivator carbonyl compounds C ₄ -C ₁₃ and 0.01-0.15 water at molar ratios of oxide: alcohol: carbonyl compound: water: aluminum chloride, equal to 4.90-5.00: 3.90-8.00: 0, 01-0.05: 0.01-0.05: 1.00, gradually fed to the cationic block oligomerizate at elevated temperature.

The authors found that using the above deactivating mixture and the conditions, cationic block telomerization of the components of the deactivating mixture with unsaturated hydrocarbons and their dimeric-make-up fraction occurs, turning them into an oil-polymer resin containing ether groups, as well as the synthesis of aluminum by organic compounds, the interaction of aluminum chloride with fragments ekzotritsiklo- [5.2.1.0 ^2.6] -dodeka-3,8-diene structures and subsequent rehybridization sp ³ -sp ² aluminum atoms, transforming strongly acidic tetrahedral omplex a neutral Lewis bipyramidal form of salt:

This probably explains the fact that the acid number (GOST 3526-89) of the KNPS thus obtained does not exceed 1.5 mg KOH / 1 g, and the water resistance is more than 480 hours at room temperature.

Thermal co-oligomerization of unsaturated hydrocarbons, their cationic block oligomerization with the obtained thermo-oligomer and the separation of KNPS by distillation of unreacted hydrocarbons are carried out under the conditions of the prototype.

Common features of the known and claimed technical solutions are signs relating to:

- feedstock, thermal and cationic (block) co-oligomerization modes;

- use of the same catalytic complex;

- modes of selection of the target product.

Distinctive essential features of the claimed invention are:

- the use for decontamination of aluminum chloride is not Brandsted, but the Lewis base of the claimed composition;

- increase in decontamination temperature to 75-90 ° C;

- gradual supply of the base to the cationic block oligomerizate;

- the exclusion of the node for water washing of the deactivate and discharge of chemically contaminated wastewater, that is, the transfer of aluminum chloride fragments to the KNPS functional group, providing such a sharp increase in the adhesion of KNPS to solid surfaces.

The presence of these distinctive features allows us to solve the problem:

- simplify the technology by eliminating the countercurrent column and sump;

- increase environmental safety by transferring it to the category of non-waste;

- increase the yield from 62.9-91.4 to 93.0-96.0% by weight of unsaturated hydrocarbons and their thermo-oligomers fed as feedstock to the cationic block oligomerization zone;

- increase the adhesion of KNPS (method of "lattice" film cuts, GOST 15140-78) from 2-3 to 1 point;

- increase the strength of the film during bending from more than 20 mm to 2-5 mm (GOST 6806-83);

- reduce the bromine number of KNPS from 25-50 to 20-24 g Br ₂ per 100 g KNPS.

The foregoing is illustrated by the following examples.

Example 1

350 g of the C ₉ fraction of flexible pyrolysis in ethylene mode, containing, wt.%, In total: 2.2 styrene, 4.8 allylbenzene, 9.3 α- and β, are loaded into a stirred reactor, thermostatted at 30 ° C. -methyl styrenes, 19.7 dicyclopentadiene (dCPD), 11.2 vinyl toluene, 18.9 indene, 20.3 alkylbenzenes, 5.0 indan, 8.6 linear and alicyclic unsaturated hydrocarbons with non-conjugated double bonds at the primary and secondary carbon atoms. 650 g of an oily product obtained by thermostating of the above C ₉ fraction at 220 ° C for 5 hours and containing, wt.%, Totaling: 29.9 dry residue, 3.7 co-dimensional trimeric fraction of thermo-oligomers, 41.1 unreacted, are introduced here unsaturated hydrocarbons, 5.0 indan and 20.3 alkylbenzenes.

With stirring, 31.5 g of a solution in xylene of a catalytic complex containing, wt%: 25.0 anhydrous aluminum chloride and 8.3 propylene oxides, is supplied here for 30 minutes. The contents of the reactor with a gradual increase in temperature to 75 ° C are stirred for 5 hours.

To deactivate the catalyst, 34.29 g of a deactivating-modifying mixture (DMS) containing, wt%, in the amount of: 49.58 propylene oxide, 49.58 n-butanol, 0.7 mixture of carbonyl compounds are fed into the reactor within 45 minutes C ₄ -C ₁₃ (acetaldol, crotonic, butyric, aniseed aldehydes, acetophenone and benzophenone with an average molecular weight of 158) and 0.14 water. After stopping the supply of DMS, the contents of the reactor are stirred for another 15 minutes Unreacted hydrocarbons are distilled off from the obtained deactivate in a stream of nitrogen at 190 ° C.

694.7 g of KNPS are obtained. The resin yield is 93% by weight of unsaturated hydrocarbons and their thermo-oligomers fed into the feed zone.

Received KNPS is characterized by:

- full transparency, as well as compatibility (1: 1 by weight) with alkyd resin PF-053, as well as with oxidized sunflower oil, characterized by a conditional viscosity of VZ-4 at 20 ° C for 180 sec, TU 38.103542-89;

- color 10 units. IMSh - GOST 19266-79;

- softening temperature (ring, ball GOST 23863-79) 81 ° С;

- bromine number 24 g Br _2/100 g;

- adhesion to metal 1 point;

- film strength at a bend of 5 mm.

Examples 2-5 (data are shown in the table)

KNPS receive and allocate under the conditions of example 1, but using as a catalyst deactivator a mixture of Lewis bases of the other claimed composition, as well as temporary and temperature decontamination modes.

In Example 2, a mixture, wt.%: 40 C ₉ fractions according to Example 1, 30 of the fraction of dCPD (wt.%: 0.3 CPD, 2.8 co-polymer CPD with isoprene, 1.5 CPD co-polymer with piperylene , 18.0 piperylene dimers, 0.4 methyltetrahydroindene, the rest dCPD) and 30 piperylene fraction (wt.%: 35.2 cis-, 51.8 trans-piperylene, 2.1 isoprene, 1.8 2-methylbutenes-1 , 2, 2.5 n-amylene, 2 methylbutene-3, 3.5 pentanes, 1.1 unidentified hydrocarbons).

In Example 3, a C ₉ -C ₁₀ fraction was used as the LSPN (boiling point 140-280 ° C, after separation of crystalline naphthalene containing, wt%: 3 styrene, 1.5 α-methyl styrene, 19.0 vinyl toluene, 11, 0 dCPD, 2.0 β-methylstyrene, 11.0 indene, 5.0 methyl- and ethylbenzenes, the rest is alkylbenzenes, methyl- and ethylindanes, naphthalene, α, β-3-alkylnaphthalenes, diphenyl, acenaphthene, fluorene, phenanthrene, anthracene , their alkyl derivatives and unidentified alkyl polynuclear aromatic hydrocarbons).

In Example 4, a C ₉ fraction of Example 1 was used.

Example 5 (comparative)

350 g of the C ₉ fraction of Example 1 and 650 g of the oily product of thermostatting of this fraction of Example 1 are charged into the reactor, but after preliminary purification and drying to trace amounts of oxygen-containing impurities. With stirring, 38.0 g of a solution of the catalyst complex is also introduced into the reactor, containing, wt%: 15.8 anhydrous aluminum chloride and 5.3 propylene oxides in xylene, purified and dried to trace amounts. After 5 hours of stirring at 30-75 ° C, 50 g of 30% aqueous sodium hydroxide are also added thereto. The mixture is stirred for 15 minutes, washed with water until a neutral reaction of the aqueous layer.

Unreacted hydrocarbons are distilled off from the hydrocarbon layer in a stream of nitrogen at 190 ° C. 355.6 g of KNPS are obtained. The KNPS yield is 47.6% of the mass of unsaturated hydrocarbons and their thermo-oligomers contained in the C ₉ fraction and the oily product of its preliminary temperature control.

The resulting resin is characterized by:

- softening temperature 50 ° C;

- bromine number 50 g Br _2/100 g SNRC;

- color 10 units. IMSh;

- full transparency and compatibility with vegetable oil and alkyd resin;

- adhesion to metal 3 points;

- strength in bending - more than 20 mm.

The amount of thermosoligomer, as well as cationic block oligomers, was determined by the solids content; hydrocarbon composition - using gas-liquid chromatography, infrared spectroscopy, proton magnetic resonance, iodine and ozonometry; microimpurity - using potentiometry.

Analysis of the results of the practical implementation of the method of obtaining KNPS shows that replacing a deactivator - a mixture of alkali and water with a mixture of the claimed composition allows you to:

- simplify the technology by eliminating the countercurrent column and sump;

- increase environmental safety by transferring it to the category of non-waste;

- increase the output of KNPS;

- increase the adhesion of KNPS;

- increase the strength of the film in bending;

- reduce the bromine number.

The results of obtaining petroleum resin Example No. The concentration of AlCl ₃ , wt.% By weight of the reaction mixture of cationic block oligomerization Catalyst Decontamination Conditions The yield of KNPS, wt.% From unsaturated y / in and their thermo-oligomers KNPS properties The component of the decontamination mixture and wt.% By weight of the decontamination mixture α The feed time and decontamination mixture, min Temperature ° C Softening point, ° С Bromine number Adhesion to metal, score Color, units IMSh The strength of the film in bending according to ShG-1, mm Flaxseed oil compatibility m Compatible with alkyd resin PF-231 one 0.8 Propylene oxide - 49.58 4.99: 3.89: 0.02: 0.05: 1 45 75 93 81 24 one 10 5 I'm full complete Butanol - 49.58 Carbonyl C ₄ -C ₁₃ - 0.70 Water - 0.14 2 1.8 Ethylene Oxide - 19.84 4.96: 7.48: 0.04: 0.05: 1 75 85 93 one hundred 21 one thirty 3 I'm full complete Isoamyl alcohol - 79.45 Carbonyl C ₄ -C ₁₃ - 0.62 Water - 0.09 3 1.4 Ethylene Oxide - 27.87 5.00: 7.65: 0.01: 0.02: 1 60 80 81 90 23 one twenty four I'm full complete Butanol - 71.98 Carbonyl C ₄ -C ₁₃ - 0.11 Water - 0.03 four 2.2 Propylene oxide - 35.88 5.00: 6.97: 0.02: 0.02: 1 90 90 96 108 twenty one 40 2 I'm full complete Butanol - 63.74 Carbonyl C ₄ -C ₁₃ - 0.34 Water - 0.04 5 (comparative) 0.8 Sodium hydroxide - 0.43 NaOH: H ₂ O: AlCl ₃ 8.17: 4166.67: 1 300 twenty 72 fifty fifty 3 10 more than e20 I'm full complete Water - 99.57

Claims (3)

1. A method of producing a petroleum polymer resin by cationic co-oligomerization of unsaturated hydrocarbons in liquid pyrolysis by-products and block oligomerization with the oily product of thermostatting of the initial fraction in the presence of a catalytic complex of aluminum chloride and an olefin oxide promoter at an elevated temperature, followed by deactivation of the catalytic complex with a base and distillation of non-reacted hydrocarbons characterized in that a mixture is used as a catalyst deactivator Lewis bases, wt.%: 20.0-50.0 olefin oxide, 50.0-80.0 alcohol C ₄ -C ₅ , 0.1-0.7 carbonyl compounds C ₄ -C ₁₃ and 0.01- 0.15 water at a molar ratio of oxide: alcohol: carbonyl compound: water: aluminum chloride, 4.90-5.00: 3.90-8.00: 0.01-0.05: 0.01-0, 05: 1.00 gradually fed to the cationic block oligomerizate at elevated temperature. 2. The method according to claim 1, characterized in that the deactivator is fed into the blockooligomerizate for 45-90 minutes. 3. The method according to claim 1, characterized in that the decontamination temperature is 75-90 ° C.