CS260341B1 - Hydrophylic naphtha nutrient and method of its preparation - Google Patents

Abstract

Illydrophilic petroleum resins can be utilized in the manufacture of dyes, varnishes, paper sizing agents, impregnating materials, adhesives 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 in a molecule with average molar weight of 360 to 1000 kg. mole-1 carboxylic acid the groups and / or anhydrides formed with maleic acid and / or anhydride thereof, in the amount that corresponds to the number 10 to 200 mg KOH.g '* 1 resin. bitumen is prepared from unsaturated fractions hydrocarbons boiling in the range of 130 to 200 Celsius degrees obtained from thermal and / or / or catalytic processing processes petroleum products at 190-260 ° C thermal by copolymerization with anhydride and / / or maleic acid and / or addition thereof products at 1 to 30% wt.

Description

The invention relates to a hydrophilic petroleum resin and to a process for its preparation.

Unsaturated hydrocarbons resulting from the thermal or catalytic treatment of petroleum fractions are most commonly used as starting materials for the production of petroleum resins. The most widespread is the use of liquid hydrocarbon pyrolysis products. These contain valuable diene, alkenyl and vinylaromatic or other hydrocarbons.

The fraction of C ₅ hydrocarbons (boiling point 30-70 ^C CJ comprising mainly isoprene, cyclopentadiene, piperylene, fraction C _M to C 9 (130-190 ° C) in turn, styrene, indene, vinyltoluene. The yield and composition of the fractions of C, - _'C to C _for liquid pyrolysis products depends on the chemical composition of the raw material and the conditions of the pyrolysis process.For the preparation of light types of petroleum resins pyrolysis fractions boiling up to 200 ° C are used and for dark types of resins higher boiling fractions or pyrolysis oils. components that can act as catalytic poisons can produce a lot of gel and deteriorate the quality of the resin, so it is advisable to remove these unwanted components prior to polymerization.Asually, if the raw material is not treated, aromatic petroleum resins are more inferior to aliphatic, especially in color This is in part due to some monomers of the conjugated polyene structure, i.e. It is therefore desirable to remove these monomers by distillation prior to polymerization in order to obtain better color resins (jap. Patent 74--99588, jap. 75-29754).

Fraction C ₃ in turn contains 5 to 20 wt. cyclopentadiene. Its polymerization produces not only a gel sentence, but also the color of the resin obtained is poor. It is common practice that cyclopentadiene is converted to dicyclopentadiene by heating, which is removed by distillation (German Patent 2,856,335). Thermal dimerization is generally carried out in two stages (Japanese Patent 75-8884), when the temperature of the dimerization is very high, it dimerizes not only cyclopentadiene but also isoprene and piperilene, and polymerization of the C ₅ fraction containing these dimers results in an alicyclic structure resin. , which resembles a terpene resin (Japanese Patent 75-17517, Japanese Patent 75-17231, Japanese Patent 74-107394).

Since this resin is miscible with natural and synthetic gums, it is used as an additive to improve adhesion properties (Japanese Patent 74-7658). Improvement of the resin colors is also achieved when the moisture in the raw material is adjusted to 150 to 800 ppm (Japanese Patent 79-4985), for example by means of molecular sieves, or when the cyclodienes are removed! by selective polymerization in the presence of BF ₃ .Et.-O and distillation (Japanese Patent 77-69995 ").

Another possibility of obtaining quality resins is the fractionation of the raw material. For example, the major monomers in the Cy fraction are viuyltoluenes and indenes. By distillation of this raw material, two fractions were obtained. Because the first fraction contains relatively few components that worsen the heat! the stability of the resin and the ability to withstand weathering, its polymerization produces good resins. The second fraction, in turn, contains a number of indenes and methylindenes, which transmit the stiffness 11a of the main chain, thus producing a nutrient with a high roiling temperature. Accordingly, by fractionating the Cy fraction, resin types with different properties can be prepared (Japanese Patent 75-33041, Japanese Patent 75-34078).

However, for many applications it is required! Resins which, in addition to the light color, also have hydrophilic properties. This is achieved by introducing polar groups such as carboxyl or hydroxyl groups into the petroleum resin molecule. Where hydrophilic resins are prepared directly by copolymerization of unsaturated hydrocarbons and / or mixtures thereof with polar monomers, these are coordinated. with a catalyst such as Lewis acid, thereby reducing the catalytic activity in its slim cases.

These drawbacks are overcome by a hydrophilic petroleum resin based on unsaturated hydrocarbons boiling in the range of 130 to 200 ° C according to the invention, which is based on a molecule with an average molecular weight of 360 to 1000 kg. mol ¹ contains carboxyl groups and / or anhydrides in an amount corresponding to an acid number of 10 to 200 mg KOH.g ^-1 resin. The process according to the invention is characterized in that the unsaturated hydrocarbon fractions boiling in the temperature range of 130 to 200 ° C obtained from thermal C / or catalytic petroleum product processing processes are thermally copolymerized with anhydrides and / or maleic acid and / or % of ethylene, propylene, butenes and / or mixtures thereof in an amount of 0.1 to 7 wt. at least 10 carbon atoms per molecule.

They are most often used for preparation! unsaturated hydrocarbon fractions obtained by pyrolysis of petrol, kerosene or gas oil. In order to obtain the petroleum resin of the desired properties, it is necessary to maintain the determination in the lymerized raw material! % of unsaturated compounds, usually 25 to 60 wt. and in specific cases the content of some olefins. The unsaturated hydrocarbon feedstock is a C ₅ fraction, a C ₈ to C ₉ fraction and various distillation slices of pyrolysis gasoline.

The ildrophilicity of the final petroleum resin is achieved by introducing polar carboxyl groups into the resin molecule. As sources of such polar groups, monomers are used which have the possibility in the po260341 process

With the lyophilization reaction incorporated into the polymeric backbone. In the present invention, we use anhydride and / or maleic acid. Adducts of these substances may also be used. The Diels-Alder reaction with dienes such as cyclopentadiene, butadiene ion, isoprene, piperilene and other olefinic compounds, either alone. or fed in a mixture, for example as present in the C ₃ fraction. The amount of these polar monomers to be used for copolymerization with the processed fraction of unsaturated hydrocarbons is dependent on the content of unsaturated hydrocarbons in the fraction and also on the desired hydrophilic properties of the final petroleum resin, in particular in terms of acid, color number, solubility in organic solvents and roakenia temperature.

Usually these substances are used in an amount of 2 to 30% by weight. calculated on the amount of olefinic feedstock to be treated. Petroleum resins having an acid number in the range of 10 to 200 mg KOH are obtained. g ¹ resin. In order to improve the quality of the resin, especially 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 anhydride and / or maleic acid monomers in the presence of ethylene, propylene, butenes and / or oligomers. mixtures thereof. These are added to the reaction mixture in an amount of 0.1 to 7 wt. calculated on the weight of the polymerized feedstock. In order to achieve the desired results using the oligomers, it is necessary that the added oligomers contain at least 10 carbon atoms per molecule, preferably 10 to 25.

The polymerization can be carried out discontinuously or continuously, while ensuring good mixing of the reactants during the reaction. The reaction proceeds at temperatures above 180 ° C, preferably at 220-250 ^° C. Higher temperatures promote the decarboxylation of polar monomers and result in a hydrophilic petroleum resin.

The reaction time depends on the composition of the reaction mixture to be treated, the reaction temperature, the degree of conversion desired and the physicochemical properties of the resin to be prepared. It ranges from 1 to 10 hours, usually 3 to 5 hedges. The course of the decarboxylation reactions indicates a gradual increase in pressure in the polymerization reactor. Upon completion of the polymerization, unreacted substances, any solvent used, are distilled off and / or stripped off with water vapor or an inert gas. The advantages of preparing a hydrophilic petroleum resin according to the invention can be seen from the following examples:

Example 1

The polymerization was carried out in a 1 dm ³ stainless steel reactor equipped with heating, a temperature controller controlled by a Fe-Ko thermocouple and a paddle stirrer to ensure the reaction mixture was stirred. 403 g of pyrolysis of gasoline boiling in the temperature range of 130 to 190 ° C, density 890 kg were weighed into the reactor. nr ³ containing 41.7 wt. of olefinic hydrocarbons and 80 g of raaleinic anhydride. While stirring, the reaction mixture was gradually heated to 230 degrees Celsius at this temperature. The mixture was stirred for an additional 4 hours. Under these conditions, the reactor pressure gradually increased from 0.6 to 1.5 MPa over a reaction time. After cooling the reactor and depressurizing. pour the liquid reaction mixture to 1 dm & lt ^; -1 & gt ^;; Three-necked flasks and hydrocarbon bags up to 150 ^° C were distilled off at normal pressure. Another portion of unreacted hydrocarbons was distilled off under reduced pressure, and dried nitrogen was introduced into the liquid mixture. The distillation was terminated at 1.50 ° C (measured in a liquid mixture) and a pressure of 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 the above reaction conditions, an oil resin was obtained in a yield of 67.2% by weight. with the following properties: ring-glove softening temperature 121 ° C, acid number 132.3 mg XOH.

. g ^-1 , average molecular weight 469 g. mol ¹ , color according to Gardner method (50 per. toluene solution) 3.

Example 2

Procedure as in Example 1, but 20 g was used for polymerization. of maleic anhydride and 10 g of maleic acid. The reaction was carried out at 250 ° C for 6 hours. By treating the reaction mixture, an oil resin was obtained in a yield of 00.6% by weight. a softening point of 103 ° C, an acid value of 58.8 and a mean mg.KOH.g ^J> with molecular weights of 402 g. mol · ¹ .

Example 3

The eye procedure of Example 1, but a fraction of pyrolysis gasoline boiling in the temperature range 135-165 ° C containing 30.6 wt. of unsaturated hydrocarbons, in quantities of 400 g and 30 g of maleic anhydride. The polymerization was carried out at 250 ° C for 5 hours. Working up of the reaction mixture gave an oil resin in a yield of 59.1% by weight. with a melt temperature of 118 ° C, an acid number of 38.4 mg KOH. g ^-1 and an average molecular weight of 569 g.

. mól ^l .

Example 4

For the polymerization, a gasoline fraction boiling in the temperature range of 135 to 200 ° C containing 1.9 wt. % dicyclopentadiene and 44.9 wt. other unsaturated hydrocarbons. To 400 g of this fraction was added 10 g of maleic anhydride and stirred with stirring at 80 ° C for 30 minutes. This resulted in the reaction of dicyclopentadiene with maleic anhydride, which was virtually quantitatively converted into the corresponding adduct.

An additional 30 g of maleic anhydride was added to the mixture, the reactor was sealed and gradually heated to 240 ° C. At this temperature, the reaction was allowed to stir for 5 hours. Further work-up, as in Example 1, yielded 47.7 wt. having a steeping temperature of 81 degrees Celsius, an acid number of 83.3 mg KOH.g ^-1 and an average molecular weight of 406 g. mól ^- '.

Example 5

The process and the hydrocarbon feedstock as in Example 1, but 60 g of maleic anhydride and 12 g of propylene oligomers boiling in the temperature range of 160 to 210 ° C were used for polymerization, with an average of 1.3 double bonds per average oligomer molecule. The reaction was run at 235 ° C for 8 hours. 206 g of a petroleum resin having a softening point of 110 DEG C., an acid number of 114.1 mg KOH.g ^-1 , an average molecular weight of 404 g, were obtained. ⁴ and color according to Gardner 3.

Example 6

Procedure as in Example 1, but 350 g of pyrolysis gasoline boiling at 130-170 ° C, 50 g of boiling at 185-195 degrees Celsius, 20 g of maleic anhydride, 6 g of propylene oligomers as in Example 5 were used for polymerization, and 4 grams of butene oligomers with an average molecular weight of 236 g.mol ^-1 . The reaction was carried out at 250 C. ^At 8 hours to give 231 g of a petroleum resin having a softening point 91 ° C and an acid number of 41.2 mg KOH.

π -1 - o ·

The hydrophilic petroleum resins prepared according to the process of the invention are well soluble in hydrocarbon and other solvents and are used in the manufacture of dyes, lacquers, refineries, impregnating materials, adhesives and many other applications.

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