SU1244161A1 - Method of joint oxidation of vegetable oils with indene-coumarone resin - Google Patents

Description

i1

Coagulation refers to methods for producing film-forming by co-oxidation of vegetable oils with inden-coumarone resin when heated in the presence of Kc (talizato-PQB. And can be used in the production of drying oils, varnishes and other paint and varnish compositions, as well as in rubber.

The aim of the invention is to increase the stability of the oxidate during storage, to improve the solubility in white spirit and to reduce its flowability, to reduce the unproductive loss of vegetable oil and to reduce the emission of volatile products polluting the atmosphere.

Characteristics of the raw materials used; second-grade technical sunflower oil, which meets the requirements of GOST 129-79, did not undergo any additional purification of cotton oil, technical in accordance with GOST 1128-75j, technical soybean oil in accordance with GOST 7825-76, indene-coumarone resin in accordance with GOST 9263-66, atmospheric air, has not been subjected to additional purification.

Catalysts: reactive purity orthophosphoric acid; sodium phosphate monosubstituted reactive purity.

  The resulting oxidates are viscous, uniform, completely transparent in a layer 15 cm thick or more from brownish red to light cherry color (depending on the content of indenomericon resin in the initial load), satisfactorily soluble in white spirit without additives. xylene and other alkyl aromatic compounds. Of these, linol-type liners and varnishes for rubber shoes are prepared using known techniques. The preparation of the specified drying oil and control over its quality indicators were carried out in accordance with

requirements of GOST 190-78 and GOST 17537-72. Black lacquer for shoes is prepared by the actualization of the oxidate, the combined oxidation of the inden-coumarone resin with vegetable oil in the presence of oil-soluble indulin as a dye and catalyst.

Example 1. 800 g of technical sunflower oil are introduced into an autoclave-type reactor with rugakoy and me612

stirring and heat with stirring to 100 ° C. Upon reaching the specified temperature after

A loading nozzle injected 200 g of indene-coupon resin of the brand in portions up to 5-10 g with an interval between the introduction of individual portions of 1-3 minutes. Upon completion of the introduction of the resin stirring is continued for another 20 minutes During this time, almost all the resin introduced goes into solution. The duration of the preparation of this solution is 85 minutes. The resulting solution of inden-coumarone smog in oil is squeezed with nitrogen into the oxidizer, which is a 1-cylinder vessel with a length-to-diameter ratio of 15, in the lower part of which is a bubbler . In front of the oxidizer, the permutable solution passes a filter in the form of a glass plate grid with holes with a diameter of 0.2-0.5 mm. This filter traps the solution along with the resin that is dosed.

coarse mechanical impurities t

After the solution is over-pressed, a small stream of air (0.2 l / min per 1 kg of load) is supplied to the oxidizer, the reaction mass is checked for foaming and the jee is heated to 25 ° C. When this temperature is reached, 1 g of orthophosphoric acid is introduced and air consumption up to 5.7 l / min per 1 kg of loading. The introduction of orthophosphoric acid is accompanied by a sharp darkening of the reaction mass and a noticeable loss of its transparency. Lo after 1.5 W there is a significant lightening of the solution and a sharp increase in its transparency. At the same time, the solution acquires a characteristic cherry-red color5, which corresponds to the full completion of the thermo-oxidative purification stage of impurities that prevent oxidation,

Under these conditions, the air is continued to bubbling for an additional 1 hour. Then, a programmed temperature decrease is carried out at a rate of 0.5 degrees / minute to 100 ° C. The air flow rate remains constant.

Upon reaching the temperature support with an accuracy of -2.5 ° C and

continue oxidation at a constant flow rate of air for another 4.5 hours. During this time, the viscosity of the oxidate rises to 5 A minutes per VZ-.4, and the samples taken during cooling and standing do not structure. Such an oxidate is quite suitable for obtaining paintwork materials from it.

Stop the flow of air and drain the oxidate into its intended container. Oxidate weight is 1012.7 g. Weight of condensed volatile products collected in a trap is 28.3 g. Number of volatile products entrained with the flow-through gas phase outside the cooler-condenser (according to the results of chromatographic analysis of the flow-through flow gas phase and weight products in a low-temperature (-50 C) trap before being released into the atmosphere) amounted to 11.5 g.

Compared with the prototype, the semi-oxidized oxidate is more soluble in ay-spirit and allows you to prepare an oxol type oxol without the addition of xiol. It is much more resistant to structuring: during storage for 2 years, no trace of formation of a solid phase was found, while in the sample according to the prototype, structuring into a block already after 0.3 months. At the same time, the quality indicators produced from oxidized drying oil (for 2 years) practically do not depend on the storage period of the oxidate until the moment of use. The solubility of the oxidate in white spirit is practically independent of this factor.

Comparison of the individual components. material balance and quality indicators obtained from oxydate paint compositions are given in Table. 4.5 and 9.

Examples 2-4. The process is carried out analogously to example 1, however, in the use of one loading in example 2, 10% by weight of indenomericon resin is contained, rto example 3-15, in example 4-30.

The temporal characteristics of the oxidative processes in stages (examples 2-4) are given in Table. one.

Examples 5-9. Raw materials, loading norms, sequence ope2441614

The radios and temperature regimes are the same as described in Example 1. Catalyst H.RO: 0.1 g (Example 5) and 1.5 g (Example 6), NaH ,, POj: 5 tO, 1 g ( example 7), 1 g (example 8) and 1.5 g (example 9).

The temporal characteristics of oxidative processes in stages (examples 5-9) are given in Table. 2. fO EXAMPLES 10 and 11. Plant. nye sunflower oil, grade A inden-coumarone resin (lower melt). Catalysts 1 g per

I kg load (example 10) and a mixture of t5 0.5 g / kg HjPO and 0.5 g / kg NaHjPO

(example 11). The sequence of operations-stages and temperature regimes, with the exception of the stage of preparing the solution of inden-coumarone resin in

20 oils are similar to those described in example 1. The solution of grade A indene-coumarone resin in sunflower oil is carried out at 70-3 ° C.

The temporal characteristics of the oxidative processes for examples 10 and

II are given in table. 3. I

Examples 12 and 13. For the oxidation, soybean (Example 12) and Hopik (Example 13) vegetable oils are used: 800 g per 1 kg of load, and indigomeric resin of mark B 200 g per 1 kg of load. Phosphoric acid catalyst 1 g per feed load 1 kg. The process is carried out similarly to 5 measure 1.

The catalyst is introduced and heated to the temperature of thermo-oxidative purification is carried out, respectively, 18 minutes in example 12 and 23 minutes in example 13).

 Thermal-oxidative cleaning in the case of soybean oil is carried out for 2.5 hours, due to the difficulties of thermal-oxidative destruction of frothers present in soybean oil in increased amounts (as compared with, for example, sunflower). Thermal-oxidative cleaning in the case of cottonseed oil is carried out at 150i5 ° C for 3 hours.

0 tjrpQ due to the high content of gossypol and other antioxidants, as well as their relatively high resistance to thermo-oxidative degradation.

5 The end of thermo-oxidative purification is fixed by abrupt lightening of the reaction mixture and the acquisition of full transparency in a layer not thick.

it is 8-10 cm. The air flow rate at the end of the thermal oxidative purification is adjusted to 6 liters per minute per kg of load and maintained until the end of the oxidation process.

Starting from the moment of the sharp lightening of the reaction mixture and the acquisition of transparency, the temperature is reduced at a rate of 1 K / min to 100 ° C with constant air flow and bubbling intensity. This operation takes 37 minutes in example 12 and 64 minutes in example 13. Next, oxidation and oxidation of viscosity will be carried out up to 53i1 minutes by VZ-4. It took 323 minutes in example 12 and 495 minutes in example 13.

Preparation of a solution of inden-coumarone resin mark in sunflower oil50

Squeezing, filtering the solution into the oxidizer and heating up to 125 C at an air flow rate of 0.2 l / min per 1 kg of load

Input catalyst (HjPO ;, 1 kg per 1 kg of load), thermo-oxidative cleaning and oxidation with

Oxidation with a programmed decrease in temperature at a rate of 0.5 deg / min

Oxidation at 100–2 ° С and viscosity set up to 53–1 min by VZ-4

The effect of the conditions of the joint oxidation of sunflower oil from 20% by weight of grade B indene-coumarone resin to the viscosity of an oxol type oxol is given in Table. 6,

The tendency of oxidatives of the joint oxidation of sunflower oil from 26.7 wt.%, The inden-coumarone resin mark in to the separation of the solid phase during storage (viscosity of oxidates 45-3 minutes) is given in table. 7

The change in viscosity of MA-22 inks made on linseed oils according to Example 3 is given in Table. eight.

The properties of black lacquer for shoes made from the oxidates of examples 2 and 3 are given in table. 9.

T a b l and c a. one

65

105

20

40

140

180

58

65

180

240

335

Preparation of a solution of indene-coumarone resin mark in sunflower oil

Squeezing the solution into the oxidizer, filtering and heating to 125 ° С 27

Catalyst input, thermo-oxidative cleaning and oxidation at 125 ° C. 195

Oxidation at a programmed decrease in temperature at a rate of 0.5 deg / min

Oxidation at 100 t2 C and a set of viscosity up to 531 M, 5 min according to VZ-4.

of indene-coumarone resin solution in sunflower oil

Squeezing the solution into the oxidizer, filtering, heating to 125 ° C. Input of the catalyst, thermo-oxidative cleaning, oxidation at 125 ° C

87

83

91

77

33

29

35

thirty

150

205

190

184

65

58

61

63

295

335

260

285

Oxidation with a pro-grammed temperature drop at a rate of 0.5 deg / min to

47

51

Oxidation at C and

viscosity set up

53tO, 5 min

317

.Table 4

The effect of the conditions of the oxidative process and the qualitative and quantitative composition of the initial load on the individual components of the material balance in examples 1-13,

Sunflower 800 N ,, 0 V 200

Also

Soy

900Too 1,

850 - 1,

700 - 1,

800 - 0.1 V 200

800 - 1,

800NaH PO O,

Sunflower 800 NaH.PO; 1.0 B 200

Also

800 1,

800 1,

800

 0,

800 1,

13 Cotton 800 N, RO. 1.0 V 200

Table 6

Ig

Viscosity of use - Viscosity of drying oil of the type oxol (with BZ-4) of oxndate, from oxidates obtained from one minute by VZ-4 and the same raw material by the method

Proposed Known Prototype

20 M, 518-19. 1A-15 11-13

50 i 2,522-25 16-18 14-16

150: 4- 20-21 18-20

Table 7.

Storage time The number of samples of 10 in which oxidate, month there was a release of the solid phase

Oxydate by pre-Oxydate by Oxydate, according to a well-known well-known prototype, by means of

About About About About About 1

 Storage Viscosity, months

0.3 I 0.5 j 0.9 2.5 5

84 95 57 88 51 107

2 8

ten

Table 8

12

123

139

131 140 157 2

Water resistance and water resistance

Frost resistance

Editor K. Voloshchuk

Compiled by 3. Komova Tehred L. Oleinik

Order 3772/27 Circulation 644Subscription

VNIIPI USSR State Committee

for inventions and discoveries 113035, Moscow, Zh-35, Raushsk nab., 4/5

Production and printing company, Uzhgorod, st. Project, 4

Tables a9

The film is water resistant and water resistant.

Meets the requirements of GOST .6410-80

Proof-reader I. Erdeyi

Claims (1)

METHOD FOR JOINT OXIDATION OF VEGETABLE OILS WITH INDENCUMARONIC RESIN when heated in the presence of a catalyst, characterized in that, in order to increase the stability of the oxidate during storage, to improve its solubility in white spirit and to reduce the emission of polluting volatile products, 0 is used as a catalyst. May 01–0.15, Z from the total load of the mixture of oil with phosphoric acid resin or monosubstituted sodium phosphate, oxidation is carried out first at 125-150 ° C for 2-3.5 hours, and then with a decrease in temperature in x Ode process with a speed of 0.5-1 deg / min to 100 * 2.5 ° C and a constant air flow rate of 5-6'l / min per 1 kg. 1244161 1 with a mechanical stirrer and heated with stirring to 100 ° C. Upon reaching the indicated temperature, 200 g of brand B ”indencumaronic resin is introduced in portions up to 5-10 g with an interval between the introduction of individual portions of 1-3 minutes through the loading pipe. Upon completion of the resin input, stirring is continued for another 20 minutes. During this time, almost all of the introduced resin passes into the solution. The duration of the stage of preparation of the specified solution is 85 minutes The resulting solution of inden-kumaro (5, a new resin in oil is squeezed with nitrogen into an oxidizer, which is a cylindrical vessel with a length to diameter ratio of 15, a bubbler is located in the lower part, 20 and the upper part is connected with a trap for low molecular weight products and a reflux condenser condenser, In front of the oxidizing agent, the squeezed solution passes through a filter in the form of a 25 glass grid plate with holes with a diameter of 0.2-0.5 mm, coarse dispersed into the solution along with the dosed resin mechanical impurities. I After completion kinked solution fed oksidator small air flow (0.2 L / min per 1 kg load), checking the reaction mixture is heated to foaming and ³⁵ to 125 ⁱⁿ jee S.Po reaching said temperature introduced 1 g of orthophosphoric acid and increase air flow up to 5.7 l / min per 1 kg load · ki. The introduction of phosphoric acid co40 is accompanied by a sharp darkening of the reaction mass and a noticeable loss of its transparency. But after 1.5 there is a significant clarification of the solution and a sharp increase in its $$ transparency. In this case, the solution acquires a characteristic cherry-red color, which corresponds to the complete completion of the stage of thermo-oxidative purification from impurities that are in the way of oxidation of ^{50 s} . Under these conditions, air continues to be bubbled for another 1 hour. Then, a programmed temperature decrease is carried out at a speed 55 0.5 deg / min to 100 ° C. The air flow rate remains unchanged. Upon reaching 100 ° C, the temperature is maintained with an accuracy of -2.5 ° C and