SU1219598A1 - Method of producing alkyd resins - Google Patents

Description

The invention relates to the field of producing alkyd resins, which are used in the manufacture of paints and varnishes for the production of protective, decorative, edisoLa1D1OH and other polymeric coatings.

The purpose of the invention is to increase the hardness and water resistance of coatings based on alkyd resins and reduce their porosity.

The bottoms of the distillation step of caprolactam production used for the preparation of alkyd resins have the following composition, wt%

Oligomers

cyclohexanone 61-66

2-Cyclohexnlidencyclohexanone12-24

Cyclohexanone1-2

Cyclohexanol 3-10

Volatile

components 2-3

Phenol1-2

Adipate sodium 2.5-8

Distillation residues are characterized by the following indicators: density (at 20 ° C) 0.98-1.02 g / cm hydroxyl number 80g200 mg KOH / g, acid number 0-5 mg KOH / g, and radion number 30-80 mg KOH / g, iodine number 20-70 mg KOH / 100 g, water content 0.5-3.0 masl.

Example 1 Synthesis alkyd i. pentaphthalic resin block method

Stage 1 Oligomerization of the bottoms of caprolactam production.

In a heated reactor equipped with a stirrer, azeotropic installation consisting of a vertical (pipe in pipe) and horizontal (for dry tubular) condensers and a separating vessel with xylene overflow lines into the reactor and the reaction water in the collection, caprolactam is discharged. The stirrer is switched on and the temperature of the reactor is raised, in the reactor at a rate of 60 degrees / h to 180 ° C5 40 degrees / to 230 ° C and 10-12 degrees / h before and held at this temperature. The resulting residue oligomerization low molecular weight products and unreacted volatile components are distilled from the reaction mass into a separation vessel (the xylene overflow line into the reactor is closed). Reaction

19598 J

considered to be complete upon receipt of the product, a 50% solution of which in vegetable oil is given indicators (viscosity ratio 32 s

5 and the content of non-volatile substances (76.1%).

Monitoring of indicators is started when the temperature of the yoke of the young mass is 230 ° C and is carried out

1C) every hour.

Then the reaction mass is cooled before and mixed with vegetable oil in the ratio of 50:50 wt.%, Which is fed into the reactor preheated 15 but heated to 1l JO-120 C. The mixture is stirred at 100-120 ° C until a homogeneous solution is obtained. The solution is cooled to 50-70 ° C and the precipitated precipitate is filtered through one stu2 (1 stump of a 42-cartridge Kuno micronage filter 125 μm (one pass through the filter), I

Stage 2 Transesterification (alcohol of vegetable oil).

25 Synthesis of alkyd resin in block form is carried out in a heated stirred tank reactor equipped with a bubbling type scavenger catcher (consisting of vertical and horizontal tube type condensers in a tube). The outlet tube of the latter is lowered into a tank filled with water.

A plant scale is loaded into the reactor, the oligomer solution obtained in stage 1 includes heating and a stirrer. The temperature in the reactor is raised to 180 ° C (60 deg / h), then the pentaerythritol and transesterification catalyst, Na COj, are loaded.

Q Continue to raise the temperature to 240-250 ° C. Algolysis of vegetable oil is carried out at this temperature. Control of the reaction is carried out according to the solubility of the sample in ethyl

41 alcohol.

Stage 3 Polycondensation. The temperature in the reactor is reduced

up to 180 ° C, charge phthalic anhydride and again raise the temperature to jg 240 ° C, collecting the resulting phthalic anhydride with hydroxyl-containing products of alcoholisation of vegetable oil with water in the scavenger, At a temperature of 240 ° C, the reaction mass is held until the specified acid number is reached and in zkosti. After that, the temperature in the reactor

The pe is reduced to 180 ° C, the mass is reacted and pumped to dissolve in a mixer that is pre-filled with an organic solvent and equipped with a stirrer.

Stage 4. Filtration of ready product.

After complete dissolution of the reaction mass, the solution (varnish) is cooled to 50-70 ° C and filtered through two stages of 42-cartridge filters Kuno, micronage: f step - 50 µm fj step - 5 µm. Through each step the varnish is passed once.

PRI mme R 2. Synthesis of alkyd glyphthalic resin block method.

The ratio of oligomerized VAT residue produced by caprolactam and soybean oil in solution is 60:40 wt.%, Respectively.

Stage 1 synthesis (preparation of a solution of oligomerized VAT residue at the distillation stage of caprolactam production) is carried out as described in Example 1. Next, the synthesis of the alkyd resin is carried out as in Example 1.

PRI me R 3. Synthesis of alkyd g pentaphthalic resin by a known method 121 azeotropic method.

Stage 1 Re-loss.

A heated reactor equipped with a stirrer and an azeotropic installation (consisting of vertical and horizontal condensers and a separating vessel with xylene discharge lines into the reactor and reaction water into the collector) is loaded with vegetable oil, bottoms of caprolactam production. Raise the temperature (60 degrees / h) in the reactor to 180 C, load pentaerythritol and soda ash. Next, raise the temperature to 200 ° C at a rate of 10-20 degrees / h, the distillation from the reaction mass of volatile components of the bottom residue, which is collected in the separation vessel (the line return xylene to the reactor is closed). Next, the temperature of the reaction mass is raised (60 deg / h) to 240-250 ° C and held at this temperature until the completion of the algolysis of the vegetable oil. In this case, the volatile components of the bottom residue, boiling away from the reaction mass at this temperature, are returned to the reactor (For

ten

15

20

2195984,

bringing the refrigerant to the vertical condenser).

Stage 2 Polycondensation. The temperature in the reactor is reduced to

5 180 C, charge phthalic and maleic anhydride, xylene. From the separation vessel, the straps of the first synthesis stage are drained and filled with xylene before the overflow (the xylol discharge line to the reactor is opened). Then the temperature in the reactor is raised to and the reaction mass is maintained at this temperature to the required acid number and viscosity. The reaction water is distilled from the reactor as an azeotrope with xylene and collected in a separation vessel.

Dissolving the reaction mass in an organic solvent is carried out as in Example 1.

Stage 3 Filtration of the finished product.

A lacquer at 50-70 C is filtered through 25 three steps of 42-cartridge filters Kuno, micronage: T stage - 125 microns (1 lacquer pass), step - 50 microns (1 lacquer pass), 111 degree - 5 microns (at least 8 passes varnish through the step to achieve the required purity).

PRI me R 4. Synthesis of alkyd glyptal resin azeotropic method.

The ratio of oligomerized VAT residue production of caprolactam and vegetable oil in plant. the thief is 55:45 wt.%.

Stage 1 synthesis (obtaining a solution of oligomerized VAT residue from caprolactam production) is carried out as described in Example 1. Next, the synthesis of the alkyd resin is carried out as in Example 3, loading the solution of the oligomerization product of stage 1 into the reactor and excluding the distillation of volatile compounds in the alkylation stage. The finished lacquer is filtered according to the method of Example 1.

thirty

35

40

45

 Ave5 Synthesis of alkyd pentaphthalic resin by a known method 1.

The synthesis is carried out analogously to example 1, starting from the stage of transesterification, but instead of the solution of the oligomerization product of stage 1 in vegetable oil, rosin is loaded into the reactor, which melts

in an ISO-ISO C reactor. After that, the agitator is turned on.

Example 6, Synthesis of alkyd pentaphthalic resin azeotropic way.

The ratio of oligomerized VAT residue of the production of lactam and sunflower oil in the solution is 60:40.

Synthesis of alkyd pentaphthalic resin is carried out according to the method of example with the difference that the exposure at the stage of oligomerization of the bottoms of caprolactam production is carried out at 230 ° C until the viscosity of the solution in soybean oil according to VZ-4 is 70 seconds. The finished lacquer has the following characteristics: viscosity (VZ-4, 20 ° C) 73.0 s, non-volatile substance content 57%, drying rate to degree 3 at 80 C 1.5 h, coating hardness M-3 0.41, other properties, like a varnish obtained in example 2.

The temperature interval of oligomerization of the bottoms of the production of caprolactam 230-250 C is determined by the stage. Oligomerization of the bottoms of caprolactam production

Temperature rise to 230 s, h min

Oligomerization at 230-250 ° С, ch.o min

Cooling to 100-120 ° С and dissolving in vegetable oil, h min

Filtration, the number of filtration stages (micron filter, microns)

Filtration duration

Number of filters used

Total stage 1 8.45-11.00

It is a chemical reaction resulting in an oligomer of inappropriate molecular weight and composition. When extracting bottoms at a temperature below 230 C, a product is obtained with a hydroxyl number of 130-140 mg KOH / G and a non-volatile content of 60-65%, since

At this temperature, the unsaturated ketones contained in the bottom residues do not enter into the reaction and alcoholysis of higher alcohols higher esters does not occur.

5 When oligomerization of bottoms is carried out at a temperature higher than 250 ° C, the resulting products are poorly soluble in vegetable oils, and in some cases insoluble in general.

In tab. 1 shows comparative data on the duration of technological processes for the preparation of alkyd resins; in tab. 2 - recipes

5 alkyd resins in the table. 3 - properties of varnishes and coatings based on synthesized resins.

.Table 1

2 stage. Transesterification

The duration of the distillation of volatile, h. Min

The duration of the stage, h.min (T, o

Stage 3. Polycondensation.

Duration, h.min

(T, O

Duration of the dissolution stage (with cooling, h. Min

Stage 4.

Number of filtration stages Micronage (µm in steps) Duration, h min

Number of used sets, pcs (at each stage)

Clear varnish after filtration

Total duration of synthesis

Continued table. one

1.00-2.00 (180-200 С)

1.00 240)

0.45-1.00 (240-250)

2.00-3.00 (250-260)

7.00-9.00 (240-250)

9.00-11.00 16.00-18.0 (240-250) (250-260)

5.00-7.00

5.00-7.00

32

125, 50.5 50.5 20.00-23.00 4.15-6.00

3-4 (1-2 stupas) 1 (3 stupas)

2-3

In the layer of varnish applied to the glass, there are no mechanical impurities and no rash, the varnish is transparent

23.30-30.30

35.45-46.00 27.15-34

.

s

18.92

23, T5

Z3.15

1.79

2.41

7,197.497 „19

8.22

12.02-15.13

0.540,691.33

46,0026, SO 46,0052.00

26.80 17.92

0.05-0.07 from the weight of quel

10.7316, T6 10.737.45

TASGLA 2

18.92

1.79

2.41

28.62

5.99 7.40

46.00

Claims (1)

METHOD FOR PRODUCING ALKIDE RESINS by reacting the bottom residue of the rectification stage of caprolactam production with vegetable oil, polyhydric alcohol and subsequent polycondensation of the obtained product with dicarboxylic acid anhydride, characterized in that, in order to increase the water resistance of the coatings based on alkyd resins and reduce their porosity, the remains of the rectification stage of caprolactam production are preheated at 230-250 ° C until a product with a viscosity of 50% solution in vegetable oil 30-70 s is obtained, mix it with 35-60% of the total load of vegetable oil in a ratio of 50-60: 40-50, respectively, and filter <g rub with subsequent introduction of the remaining amount of vegetable oil and other components of the reaction mixture. >