CS260341B1 - IlydroTile oil iiivica and the salvation of its preparation - Google Patents

Abstract

Hydrophilic petroleum resins can be used in the production of dyes, varnishes, paper sizing agents, impregnating materials, adhesive additives and the like. The essence of the solution is a petroleum nutrient based on unsaturated hydrocarbons with boiling points of 130 to 200 °C containing in a molecule with an average molar mass of 360 to 1,000 kg mol-1 carboxyl groups and/or anhydrides formed with maleic acid and/or its anhydride, in an amount corresponding to an acid number of 10 to 200 mg KOH.g'* 1 resin. The resin is prepared from unsaturated hydrocarbon fractions boiling in the range of 130 to 200 degrees Celsius obtained from thermal and/or catalytic processes of processing petroleum products at 190 to 260 °C by thermal copolymerization with anhydride and/or maleic acid and/or their addition products in an amount of 1 to 30% by weight.

Description

2 6 O 341

BACKGROUND OF THE INVENTION The present invention relates to a hydrophilic petroleum resin for its preparation.

The feedstocks used for the production of resinous resins are most often the use of non-saturated hydrocarbons produced by the thermal or catalytic processing of petroleum fractions. The most widespread is the use of liquid hydrocarbon pyrolysis products. These include valuable diene, alkenyl, or other hydrocarbons.

The C5 hydrocarbon fraction (boiling point 30 to 70 CCJ contains mainly isoprene, cyclopentadiene, piperylenes; CM to Cf fraction) (130 to 190 [deg.] C.) in turn styrene, indene, vinyltoluenes. the pyrolysis products depend on the chemical composition of the feedstock and the conditions of the pyrolysis process. For the brightest types of petroleum resins, pyrolysis fractions boiling up to 200 ° C are used, and the dark types of resins have higher boiling fractions and bopyrolysis oils. Often, petroleum resin feedstocks contain components that can act as catalytic poisons, can produce much gel, and impair the quality of the resin. Therefore, it is desirable to remove any component prior to polymerization. Usually, when the aurora does not treat, the aromatic petroleum products are inferior to aliphatic, especially in terms of color. In part, this is due to some conjugated polylene monomers found in the fraction and which polymerize. It is preferred to remove these monomers by distillation prior to polymerization in order to obtain a better color (Japanese patent 74-99588, Japanese patent 75-29754).

In fact, fraction C3 contains 5 to 20% by weight of cyclopentadiene. Its polymerization produces not only a lot of gel, but also the color of the lived is bad. It is common practice to convert the cyclopentadiene into dicyclopentadiene by heating, which is removed by distillation (NSR Patent 2,856,335). The thermal dimerization is usually carried out in two stages (Japanese Patent 75-8884). If the dimerization temperature is very high, it not only diminishes cyclopentadiene, but also iso-prene and piperilene. The polymerization of the C5 fraction containing these dimers then forms a resin with an alicyclic structure that resembles a terpene resin. (Japanese Patent 75-17517, Japanese Patent 75-17231, Japanese Patent74-107394).

Since this resin is miscible with natural and synthetic rubber, additional adhesion properties are used (Japanese patent 74 -7658). We will improve the color of the resin even if the moisture content is 150 to 800 ppm (eg, Japan patent79-4985), for example with molecular sieves, if the cyclodiene is removed! by selective polymerization in the presence of BF3.ENO and distillation (jap. patent 77-69995). Another possibility of obtaining quality of life is to fractionate the raw material. For example, the major monomers in the Cy fraction are vinyl and indenes. Distillation of this raw material yields two fractions. Since the first weave contains relatively few components which deteriorate the thermal stability of the resin and the ability to cope with the weathering, its polymerization produces high quality bitumen. The second fraction contains in addition indene methylindenes which transfer the stiffness of the 11th chain to form a high resin. by the soak temperature. Accordingly, by fractionation of the Cy fraction, resin types with different properties can be prepared (Japanese patent 75-33041, Japanese Patent 75-34078).

However, for many applications, heat is required which, in addition to light color, also has hydrophilic properties. This is achieved by introducing polar groups, for example carboxyl, hydroxyl or hydroxyl into the oil resin molecule. When hydrophilic resins are prepared directly by copolymerization of unsaturated carbonates and / or mixtures thereof with common monomers, they are coordinated with a catalyst, such as a Lewis acid, to reduce catalytic activity in many cases.

These drawbacks are eliminated by a hydrofluoric resin based on unsaturated hydrocarbons having a boiling point of 130 to 200 [deg.] C. according to the invention, the principle being that in a molecule with an average molecular weight of 360 to 1000 kg. mole "1 contains carbonyl groups and / or musk anhydrides which correspond to an acid number of 10 to 200 mg of KOH.g -1 resin. The nature of the process for preparing hydrophilic petroleum resins is that unsaturated fractions of hydrocarbons boiling in the pulse interval from 130 ° C to 200 ° C, obtained from thermal or catalytic processes of the processed products, are thermally hydrolyzed with anhydride and / or maleic acid and / or their addition products in an amount of 1 to 30% by weight, with In addition, oligomers of ethylene, propylene, butenes and / or mixtures thereof in an amount of 0.1 to 7% by weight which contain at least 10 carbon aions in the molecule can be added.

Most often, unsaturated hydrocarbon fractions obtained by the pyrolysis of gasoline, kerosene or gas oil are used. In order to obtain the petroleum resin of the desired properties, it is necessary to maintain a certain concentration of unsaturated compounds, usually 25 to 60% by weight, in the lyophilized feedstock. and, in specific cases, the content of some olefins. the unsaturated hydrocarbon cure uses a C5 fraction, a C8 to C9 fraction, and various pyrolysis gasoline distillation cuts.

The hydrophilicity of the final oil resin is achieved by introducing polar carboxyl groups into the resin molecule. The sources of such polar groups are monomers which can be incorporated into the polymer chain in the lywerization reaction process. According to the invention, it is used: anhydride and / or maleic acid. Adducts of these substances can be used, too! e.g. Diels-Alder reaction with dienes such as cyclopentadiene, butadiene imine, isoprene, piperilene and other olefinic compounds, either alone. or " in the mixture, for example, as present in the C3 fraction. The amount of these polar monomers used to co-polymerize the fraction of unsaturated hydrocarbons, depending both on the unsaturated hydrocarbon content of the fraction and the desired hydrophilic properties of the final petroleum resin, especially in terms of acidity, color, organic solubility. solvents and melting temperatures.

Usually these substances are used in an amount of 2 to 30% by weight. calculated on the amount of processed olefinic feedstock. In this context, petroleum resins are obtained whose acid number is in the range of 10 to 200 mg KOH. In order to improve the quality of the resin, particularly in terms of its solubility in organic solvents and miscibility with other polymeric materials, it is preferred to carry out copolymerization of unsaturated hydrocarbons with polar monomers on the base anhydride and / or maleic acid in the presence of The oligomers of ethylene, propylene, butenes and / or mixtures thereof are added to the reaction mixture in an amount of 0.1 to 7% by weight, based on the weight of the polymerized feedstock. that the added oligomers contain at least 10 carbon atoms per molecule, preferably from 10 to 25 carbon atoms.

The polymerization can be carried out discontinuously or continuously, while ensuring good mixing of the reactants during the reaction. The reaction takes place at temperatures higher than 180 ° C, preferably at 220 to 250 ° C. Higher temperatures promote the decarboxylation of polar monomers and the resultant hydrophilic resin.

The reaction time depends on the composition of the treated reaction mixture, the reaction temperature, the desired degree of conversion and the physicochemical properties of the feed. It ranges from 1 to 10 hours, usually 3 to 5 hours. The progress of the decarboxylation reaction indicates a gradual increase in pressure in the polymerization reactor. At the end of the polymerization, the unreacted substances, the solvent used, if necessary, are distilled off and stripped with aqueous steam or an inert gas. The advantages of preparing a hydrophilic petroleum method according to the invention are shown in the following examples: Example 1

The polymerization was carried out in a 1 dm3 stainless steel reactor equipped with heating, a temperature controlled thermostat with a Fe-K 0 thermocouple and a paddle stirrer to ensure mixing of the reaction mixture. The reactor was charged with 403 g of pyrolysis benzine boiling at a temperature of 130-190 ° C C, density 890 kg. No. 3 containing 41.7 wt. olefinic hydrocarbons and 80 g of ralaneine anhydride. While stirring, the reaction mixture was gradually warmed to 230 degrees Celsius and stirred at this temperature for an additional 4 hours. Under these conditions, the reactor pressure increased gradually from 0.6 to 1.5 MPa with the reaction time. After the reactor was cooled and depressurized. the liquid reaction mixture was transferred to 1 major three-necked flask and the hydrocarbons at 150 ° C were distilled off under normal pressure. Another portion of the unreacted hydrogen peroxide was distilled off under reduced pressure, and dried nitrogen was fed to the liquid mixture. The distillation was terminated at 150 ° C (measured in a liquid mixture) and the pressure was 1.3 kPa. The remaining contents of the flask, i.e. the petroleum resin, were poured hot into the prepared vessel, cooled, weighed and subjected to physico-chemical evaluation after homogenization. Under these reaction conditions, an oil resin was obtained in a yield of 67.2% by weight. with the following characteristics: ring temperature - ring temperature 121 ° C, acid number 132.3 mg XOH. . g '1, average molar mass 489 g. 1 ", color using the Gardner Stage method (50p. toluene solution) 3. Example 2

The procedure as in Example 1, but 20 g of maleic anhydride and 10 g of maleic acid were used for the polymerization. The reaction was carried out at 250 ° C for 6 hours. with a tapping temperature of 103 [deg.] C., an acid value of 5.8.8 mg.KOH.g " and an average > mole weight of 402 g.

The procedure as in Example 1, but for the polymerization, was a pyrolysis gasoline fraction boiling at a temperature range of 135-165 ° C, containing 36.6 wt. unsaturated hydrocarbons, 400 g and 30 g maleic anhydride. The polymerization was carried out at 250 ° C for 5 hours. The work-up of the reaction mixture gave an oil resin of 59.1% by weight. with a dropping temperature of 118 ° C, an acid number of 38.4 mg KOH. g'1a with a mean molecular weight of 569 g. mole 1. Example 4

For the polymerization, a py-

Claims (3)

2.3 Π 3 4 I of gasoline boiling in a temperature range of 135 to 200 ° C containing 1.9% by weight di-cyclopentadiene and 44.9 wt. other unsaturated hydrocarbons. To 400 g of this fraction was added 10 g of maleic anhydride and mixed for 30 minutes with stirring to 80 ° C. This resulted in the reaction of dicyclopentadiene with maleic anhydride, which was converted quantitatively into the corresponding adduct. To this mixture was added an additional 30 g of maleic anhydride, the reactor closed and gradually heated to 240 ° C. The reaction was stirred at this temperature for 5 hours. Further work-up, as in Example 1, gave an oil resin in 47.7% yield. with a cellulosic temperature of 81 ° C, an acid value of 83.3 mgKOH.g_J and an average molecular rot of 406 g. mol- '. EXAMPLE 5 The procedure and hydrocarbon feedstock as in Example 1, but 60 g of maleic anhydride and 12 g of oligomers of propylene boiling in a temperature range of 160 to 210 ° C, with an average content of 1.3 double bonds per average molecule of oligomer, were used for polymerization. The reaction was run at 235 ° C for 8 hours. 206 g of petroleum gas having a pellet temperature of 110 C were obtained, with an acid number of 114.1 mg KOH.g-1, an average molecular weight of 404 g. Example 6 The procedure as in Example 1, but 350 g of a pyrolysis gasoline fraction boiling in the range of 130 to 170 ° C, 50 g of a fraction boiling in the range of 185 to 195 degrees Celsius, 20 g were used for the polymerization. g of maleic anhydride, 6 goligomer propylene as in Example 5 and 4 g of butene oligomers with an average molecular weight of 236 g. The reaction was carried out at 250 ° C for 8 hours, yielding 231 g of petroleum resin with a temperature of 91 ° C and an acid number of 41.2 mg KOH. Hydrophilic petroleum resins prepared according to the invention are good soluble hydrocarbon and other solvents and are useful in the manufacture of dyes, lacquers, glues, impregnating materials, adhesion promoters and in many other applications. OBJECT A hydrophilic petroleum resin based on unsaturated hydrocarbons having boiling points of 130 to 200 ° C, characterized in that it has a molecular weight of between 360 and 1000 kg in the molecule. mole-1 contains carboxyl groups and / or anhydrides formed with maleic acid and / or its anhydride, in an amount corresponding to an acid number of 10 to 200 mg KOH. g-1 resin. 2. A process for the preparation of hydrophilic crude oil according to claim 1 from unsaturated fractions of hydrocarbons obtained from thermal and / or catalytic processing of petroleum products, characterized by the invention and / or unsaturated hydrocarbon fraction boiling. at a temperature in the range of 130 DEG to 200 DEG C. and thermally copolymerized with an anhydride and / or maleate acid and / or their addition products at a temperature of from 190 to 260 DEG C. in an amount of from 1 to 30% by weight. wt. are based on the weight of the non-saturated hydrocarbon fraction. 3. A process according to claim 2, wherein from 0.1 to 7% by weight is added to the reaction system. ethylene, propylene, hutene and / or mixtures containing at least 10 carbon atoms in the molecule. Severografia, n. P. Plant 7, Most Price 2,40 Kcs