SU1065435A1 - Process for producing petroleum polymer resin - Google Patents

Abstract

METHOD OF OBTAINING OIL POLYMERIC RESIN by thermal polymerization of unsaturated hydrocarbons containing esters. kip 120-200 C gasoline gas mixture go fractions with t. Kip. 150 190 C gasoline pyrolysis products under pressure in the presence of 8-20% by weight of the raw material of the modifying additive, characterized in that, in order to obtain a light resin with improved properties, as well as to increase its yield, divinyl-perylene is used as a modifying additive rubber with a molecular weight of 1500-5000.

Description

35

U1

4 ZtS U1 The invention relates to the production of petroleum resin (PS) by polymerization of liquid products of the pyrolysis of petroleum feedstock can be used in the refining and chemical industries to produce resins intended for use in paints and varnishes. A known method for producing a petroleum resin by thermal polymerization under pressure of a fraction of liquid products of hydrocarbon pyrols in the presence of 1-5% by weight of the initial fraction of polyethylene mol. weighing 200-2000 {1. The yield of the resins obtained by this method is low and amounts to 32.8-43.5%. Resins are hardly soluble in aliphatic solvents. Films based on them are opaque, which limits the possibility of using these resins in paints and varnishes. The closest to the proposed by the technical essence and the achieved result is a method of obtaining a petroleum resin by thermal polymerization of non-specific hydrocarbons contained in the bale fraction, 120-200 c. Of pyrolysis products of a mixture of gasoline and gas or a batch with miter. 150-190 ° C of gasoline pyrolysis products, under pressure in the presence of 8-20% by weight of the raw material of the modifying additive — bottom residues decomposition of dimethyldioxane 2. However, the known method provides for obtaining a resin for tire and rubber industry. Only dark resins can be obtained by this method (with a color on an iodometric scale above -200 mg iodine / 100 ml). The semi-emit dark resins are already embedded in the very essence of this method, namely, the use of dimethyl dioxane as an additive for the bottoms decomposition residues, represented a concentrate of terpene fragments and very dark products (color on HMSM over 800 mg hr / 100 lsh ). Light resins (with color up to 100 mg iodine ioo ml) by this method of production can be. The resins obtained by this method have a high unsaturation (iodine number of 84–94 g of iodine / 100 g), and as a consequence of the low elasticity of films obtained based on this petroleum Cgmole (PS) 20 mm. This indicates unsatisfactory plasticity of the PS, despite the fairly low softening temperature (87 C) In the known method, when polymerization of the 120-200C fraction, 48 wt.% Of unsaturated hydrocarbons are involved in the resin and when using the fraction 150-190 ° С 51.1 1% The purpose of the invention is to obtain a light petroleum resin with improved properties, as well as to increase its yield. This goal is achieved by the fact that according to the method of obtaining a petroleum resin by thermal polymerization of unsaturated hydrocarbons contained in the fraction with m.kip. 120-200c pyrolysis products of a mixture of gasoline and gas ip fraction with t. Kip. 150-190 With the products of gasoline pyrolysis, under pressure in the presence of 8-20% by weight of the raw material of the modifying additive, as the last used divinylpiperylene rubber with mol. weight 1500-5000 .. Resins obtained by this method have high performance (UV resistance, good color and plastics). With the introduction of molecular rubber or oil polymer to 8 wt.% Of the initial fraction, the desired effect in terms of increasing the yield and increasing the stability of the PS to UV exposure is not achieved. The introduction of more than 20% of low molecular weight rubber or petroleum polymer is impractical because the temperature of the NPC softens sharply and the hardness of coatings of paints and varnishes based on these NPS decreases. Below are examples of the production of petroleum resin by the proposed method in a laboratory autoclave with a capacity of 2 liters, equipped with a stirrer and electrically heated. The low molecular weight synthetic divinyl-psterylene (SKDP-N) used as an additive to the polymerizable raw material is a viscous mass of light yellow color with a mol. with a mass of 1,500–5,000 and a dynamic viscosity (at 25 C) of 70–140 P. The initial fraction was the fraction 120200c of products from the pyrolysis of a mixture of gasoline and gas and a fraction 150-190; gasoline pyrolysis products: Fractions Fractions 120-200 ° С 150-190 ° С Density, °, 9120,920 Iodine number, g of iodine 100 g pr.10265; The viscosity is kshematicheskii with, eats1,1 "01,204 Hydrocarbon composition of the original Fractional Fractional 120-200 t 150-1 C -, {olefins) C (dienes) CQ (olefins) Cg (paraffins and oil) 0,40,3 0,90 , 8 Xylenes + ethylbenzene оС -Metylstyrene DCPD-f-vshgaltoluene Cg saturated S. and higher. For comparison in the same laboratory autoclave, petroleum resins were obtained from the fraction of the given qualities by thermal polymerization. Example 1. 1000 g of the 120–200 C fraction of gasoline and gas pyrolysis products are loaded into a laboratory autoclave, 80 g (8 wt.%) Of low molecular weight rubber are added, and polymerization is carried out at 25 pressure 9 atm for 6 hours. with a residual pressure of 2 mm Hg. Art. liquid hydrocarbons are distilled off to 335 ° C (under normal conditions), resulting in a residue of 574 g of a thermolab resin, which is 53.1 m per polymerisable feedstock. The conditions of the obtained resin are given in table. 1. Example 2. 200 g (20 wt.%) Of low molecular weight rubber are added to 1000 g of the 12 200 ° C fraction of gasoline and gas pyrolysis products. The mixture is polymerized under the conditions of Example 1. After distillation at a residual pressure of 2 mm Hg. Art. liquid hydrocarbons get 694 g (58 wt.% on the polymerized raw materials) petroleum resin. Example 3. A mixture consisting of 1000i fraction 120-2000 ° C of gasoline and gas pyrolysis products and 120 g (12 wt. 7%) low molecular weight rubber is subjected to polymerization under the conditions of example 1, after which the non-pereusible hydrocarbons are distilled off to a terahert. In the residue, 635 g of petroleum resin or 56.7 wt.% On the polymerizable raw material is obtained. Example 4. 1000 g of a 150-190 ° C fraction of gasoline pyrolysis products with the addition of 120 g (12% by weight) of low molecular weight are subjected to polymerization at 250 ° C. Pressure of 6 atm. For 6 hours. From the obtained polymerizate liquid hydrocarbons are distilled at 374 ° C obtaining in the balance of petroleum resin in the amount of 665 g or 59.4 wt.% on the polymerizable raw materials. Example 5. To 1000 g of the 150 190 ° C fraction of gasoline pyrolysis products, 120 g (12% by weight) of liquid petroleum polymer are added and polymerized under the conditions of Example 4. At 375 ° C, liquid hydrocarbons are distilled off from the polymerizate. until a petroleum resin is obtained as a residue, the yield of which is 661 g or 59.1% by weight on the polymerizable raw material. In tab. 2 shows the potential content of resinous components and the yield of petroleum resins. From the table. 2 data shows that the proposed method allows to increase the yield of petroleum resin in comparison with the known ones: using fraction 120-. 200 C from 48 wt.% To 56.7 wt.% On polymerizable raw materials; when using fractions 150190С from 51.1 wt.% to 59.4 wt.% on the polymerized raw materials. In tab. 3 shows the component composition of the initial fractions and data on hydrocarbons entering into the polymerization; in tab. 4 quality indicators of petroleum resin. The present invention provides light petroleum resins with improved properties and increased yield.

Table 1

250

1120-200

Potential content of resin-forming components

wt.%: 58,5

Conversion% 82.1

The output of the NPS on the raw materials,

weight.%

48

335

53.1

table 2

70.5

78.9 90.1

84.3

56.7

59.4

C; 1. (Olefyshy)

0.2 C: (dieny)

0.1

C ,, (olefins) 0.5

Cg (paraffins 4shfteny0, 1

Q3

Benzene

0.4

0.9

0.8

Toluene

Xylenes + ethyl7, 2 benzene29.9 3.024.9 ot -Metylstyrene3.4 6.82.1 DCPD + vinyl27, 67.5 toluene8.3 Inden18.0 29.512.8 Cg saturated8.4 19.4-. C,., And above 1.8 5.5 Of this unsaturated hydrocarbon. 58.5 66.948.0 Low molecular weight synthetic divinylpipertenovic - rubber} tk

Table 3

0.2 100 0, 2 100

- 0.1100

OD 100

- 0,480

0.4 80 882,790,026,494,22,893,3 613,348,52,779,44,058,5 9024,388,07,590,424,388.0 1,120,870,516,491,126,790,5 - ---. - --- - 82, 151,176,453.7 91,757,886.7 -, 8 81.5 8.7 72.6

760

93

83

965

Table 4

45

40

Neutral30

thirty

Claims (1)

METHOD FOR PRODUCING OIL-POLYMER RESIN by thermal polymerization of unsaturated hydrocarbons contained in a fraction with so-called bale. 120-200 ° C of a mixture of gasoline and gas or fraction with t. Kip. 150 - 190 ° C of gasoline pyrolysis products, under pressure in the presence of 8-20% by weight of the feedstock of the modifying additive, characterized in that, in order to obtain a light resin with improved properties, as well as to increase its yield, divinyl piperylene is used as the modifying additive rubber with a molecular weight of 1500-5000.