SU1715388A1 - Method of preparing dispergator for polyvinylchloride materials - Google Patents

Description

This invention relates to a process for the preparation of a dispersant for porous polyvinyl chloride (PVC) materials, including artificial leather, based on calcium alkylbenzenesulfonate (ABSC).

A known method of producing dispersant is porous for porous PVC materials based on ABSC. comprising mixing the alkylbenzene sulfonic acid with a low molecular weight alcohol solvent, neutralizing the resulting suspension of calcium hydroxide solution (lime milk) at 20-50 ° C, centrifuging the resulting slurry of inorganic salts, drying and concentrating the purified solution of the desired inorganic salts, drying the wet-distilled alcohol and purification water layer from the alcohol dissolved in it. The resulting solution of ABS in low molecular weight alcohol (isobutanol), containing 50% by weight of ABS, is a finished product and is used as a dispersant in the manufacture of porous PVC materials,

The disadvantages of this method include the multistage process, as well as the use of isobutanol, which is a highly toxic and flammable product, as the solvent ABCS.

Closest to the present invention is a method for preparing a dispersant for porous PVC materials, comprising mixing an alkyl benzene sulfonic acid with a solvent, followed by neutralization by heating the resulting mixture with anhydrous oxide or calcium hydroxide, separating the solid phase and drying the finished product. The process of obtaining a dispersant in: go by treating anhydrous alcohol (butanol) suspension of calcium oxide or calcium hydroxide with alkyl benzene sulfonic acid in the presence of inorganic halides at 70-110 ° C for 45 minutes, followed by separating inorganic salts and distilling water from the resulting solution. The finished product is a 67% solution of ABSC in butanol.

The disadvantages of this method include using as a solvent for ABSCs highly toxic and flammable alcohol, butanol, as well as a high consumption of the resulting product in compositions to obtain porous PVC materials.

 the invention is to reduce the concentration of ABS in the finished product while maintaining its effectiveness as a dispersant, as well as simplifying the process flow diagram.

The chipping goal is achieved by the fact that according to the method of producing a dispersant for porous PVC materials, including the process of mixing ABS with solvent, followed by neutralization of the mixture obtained by heating with anhydrous oxide or calcium hydroxide and separating the teiepAOft phase from the resulting dispersant solution, distillation residues are used as a solvent

glycols or their simple zvir with their ratio to ABBS 6-7: 4-3 and the neutralization process is carried out at 70-80 ° C without removing water after separation of the solid phase from the resulting solution.

PRI me R. In a flask with a capacity of 1 l with a stirrer and a thermometer was loaded 100 g of technical ABC containing 88 wt.%. ABBS 2.0 wt.% Sulfuric acid and 10 wt.% Paraffins, 233 g of bottoms of butyl cellosolve-butyl carbitol production (ratio to ABSK 2.33: 1) were added, containing, wt.%: Butyl cellosol in 2.72; ethylene oxide 0.11; butyl alcohol 0.16; monoethylene glycol 2.98; buty l car bito l 84.34; diztilyl glycol 5,39; triethylene glycol monobutyl ether 3.62; unidentified impurity 0.68. The resulting mixture was stirred, heated to 70 ° C and neutralized with 13.8 g of anhydrous calcium hydroxide (fuzz) for 30 minutes. The temperature of the reaction mixture rose to 80 ° C. The resulting neutralized mixture was filtered and obtained a solution of ABSC 3 bottoms produced by butyl cellosolve-butyl carbitol, containing 31% by weight of the basic substance and about 2% by weight of water.

The compositions used bottoms are given in table.1.

The rest of the experiments were carried out similarly to that described and their results are summarized in table 2.

The bottoms of the production of propylene glycol corresponded to TU-6-01-124980, and the bottoms of the production of glycols and cellosolva —TU 6-01-1352-88 and had the following physical properties: density at 20 ° C, respectively, 1.05; 1.16 and 1.02; the boiling point is 160, 172 and 152 ° С.

Experiment 10 was carried out with the same bottoms as experiment 6.

: Samples 1-13 of the mixture to obtain leather include the following components, MD;

PVC resin100

brand C-70

Dioctyl phthalate 70

Chalk chemical

Azodicarbonamide3

Silicate svmntsa3

Calcium stearate 1

Barium-cadmium-lead stabilizer Stearin0,5

Dispersant for examples 1-10 tabl.20.1

As a basic object, a dipper is used, which is an industrial disperser ABSK - 50% solution ABBS in isobutanol (sample

eleven).

V.3 shows data on the effectiveness of dispersants for the preparation of vi. nilskozhi.

As can be seen from the dispersant data given in Table 3, the concentration of ABSA in a solution of bottoms production of glycols or their ethers (30.6-39.9 wt.%) Is 10-20% lower than in the dispersant produced by industry 0 %), while such a dispersant, with the same mass flow rate, in its compositions for the preparation of porous PVC materials, has the same, and in most cases, even higher dispersing ability. The decrease in the concentration of ABSC in the solution below that proposed (sample 6) gives worse results than an industrial dispersant. The increase in the concentration of ABSC in the solution of the bottoms of the production of glycols or their ethers above the proposed economically impractical.

Neutralization of ABS with anhydrous oxide or calcium hydroxide in the bottoms of the production of glycols or their ethers at a temperature below 70 ° C is very slow (practically does not proceed) and the temperature rises to 80 ° C during the neutralization process itself due to the heat of reaction. To raise this temperature due to the supply of heat from the outside is impractical.

The proposed dispersant is much less toxic and flammable than the dispersant produced by the industry. So. A 30% solution of ABSC in the bottoms of the production of butyl celloslose-butylcarbitol has a flash point of + 104 ° C, and a solution of ABBS in the bottoms of the production of propylene glycol I29 ° C, while the 50% solution of ABBS and isobutanol produced by industry has only + 29 ° C.

Simplification of the technology for obtaining the proposed dispersant due to the lack of

the stage of drying the finished product .., drying the distilled wet alcohol and the stage of purification of the distilled water layer Qiir of the alcohol dissolved in it (according to the known method, butanol or isobutanol-water heteroazeotrope separation is necessary. This results in the above steps).

Formulas Ai 3 Acquisition Method for the preparation of a dispersant for porous polyvinyl chloride materials

mixing technical alkylbenzenesulfonic acid with a solvent class of alcohols.

neutralization of the mixture with anhydrous oxide

or calcium hydroxide at 70-80 ° C, followed by filtration of the precipitate using a filtrate as the final product, characterized in that, in order to reduce the consumption of alkyl benzene sulfonic acid and simplify the technology, the residue from the production of propylene glycol is used as a solvent. containing propylene glycol 5-30 wt.%, DI-, tri-, tetrapropyleneglycol and impurities - the rest, or bottoms

the production of glycols and cellosolve containing ethylene glycol and ethyl cellosolve 1-15 wt.%; oligomers with a degree of yligomerization of 2-6 and impurities - the rest, or distillation residues from the production of butyl cellosolve-butyl carbitol, containing butyl cellosol sol in 0.2-3 wt.%, butyl esters of DI-, tri- and tetraethylene glycols and impurities - the rest, at a weight ratio of bottoms, residue; sulfonic acid

(1.5-2.33): 1.

-k Experience Production Name Butylcell Butilcarb Butylcell Butilcar Propylene Glycols and

.

Composition, wt.% Butyl cellosolv 2.72; ethylene oxide 0.11; butyl alcohol 0.1b; monoethylene glycol 2.98; butylcarbitol 8, diethylene glycol 5.39; triethylene glycol monobutyl ether 3.62; unidentified impurity 0.68. Butylcellosolve 0.2; ethylene oxide 0.08; butyl alcohol 0.12; monoethylene glycol 3.01; butylcarbitol 83.5b; diethylene glycol 6, triethylene glycol monobutyl ether 5.81; unidentified impurity 0.88 Vutyl cellosolv 3.0; ethylene oxide 0.10; butyl alcohol 0.12; monoethylene glycol 3.36; butylcarbitol 81.79; diethylene glycol 5.29; triethylene glycol monobutyl ether, b9; unidentified impurity 1.65. Propylene glycol 8.1; dipropylene glycol 79.82; tripropylene glycol and higher adducts 11.95; water 0,13 Propylene glycol 5,0; dipropylene glycol 71.21; tripropylene glycol and higher adducts 23, water 0.05. Propylene glycol 29.8; dipropylene glycol 58,89; tripropylene glycol and higher adducts 11,21; water 0.10. Ethylene glycol 8.1; ethyl cellosolve 0.1; ethyl carbitol 8.37; diethylene glycol, 83; triethylene glycol ethyl ester 13.96; triethylene glycol 23.63; tetraethyleneglycol 21.93; higher adducts 19.0; water 0.08 Ethylene glycol 0.98; ethyl cellosolve 0.02; ethyl carbitol 7, diethylene glycol 5.01; ethyl ether triethylene glycol 15, triethylene glycol 27,11; tetraethyleneglycol 28,17; water 0.10 Ethylene glycol 13.50; ethyl cellosolve 1.50; ethyl carbitol 9.01; diethylene glycol, triethylene glycol ethyl ether 11,17; triethylene glycol 23,13; tetraethyleneglycol 22,12; higher adducts And, 53; water 0.10,

Continued table. 2

Continued table. 2

Spreadsheets

Claims (9)

Formulas of the invention A method for producing a dispersant for porous polyvinyl chloride materials by mixing technical alkylbenzenesulfonic acid with a solvent of the alcohol class, neutralizing the mixture with anhydrous oxide or calcium hydroxide at 70 ~ 80 ° C, followed by filtering out the salt precipitate using the filtrate as the final product, characterized in that, with In order to reduce the consumption of alkylbenzenesulfonic acid and simplify the technology, bottoms of propylene glycol production containing living propylene glycol 5-30 wt.%, di-, tri-, tetrapropylene glycols and impurities - the rest, or bottoms from the production of glycols and cellosolves containing ethylene glycol and ethyl cellosolve 1-15 wt.%; oligomers with a degree of Oligomerization of 2-6 and impurities - the rest, or bottoms of the production of butyl cellosolve-butyl carbitol containing butyl cellosolve 0.2-3 wt.%, butyl esters of di-, tri- and tetraethylene glycols and impurities - the rest, with a weight ratio of bottoms : technical sulfonic acid (1.5-2.33): 1. th ~ Experience Name of production ___ T_a_b_l_i_ts_a__1 Composition, wt.% 1 Butyl cellosolvol-butylcarbitol 2 same 3 Butyl cellosolvol-butylcarbitol Butyl cellosolve 2.72; ethylene oxide 0.11; butyl alcohol 0.16; monoethylene glycol 2.98; butylcarbitol 84.34; diethylene glycol 5.39; triethylene glycol monobutyl ether 3.62; unidentified impurity 0.68. Butyl cellosolve 0.2; ethylene oxide 0.08; butyl alcohol 0.12; monoethylene glycol 3.01; butylcarbitol 83.56; diethylene glycol 6.34; triethylene glycol monobutyl ether 5.81; unidentified impurity 0.88 Butyl cellosolve 3.0; ethylene oxide 0.10; butyl alcohol 0.12; monoethylene glycol 3.36; butylcarbitol 81.79; diethylene glycol 5.29; triethylene glycol monobutyl ether 4.69; unidentified impurity of 1.65. 4 Propylene glycol 5 The same Propylene glycol 8.1; tripropylene glycol and water 0.13 Propylene glycol 5.0; tripropylene glycol and water 0.05. dipropylene glycol 79.82; higher adducts 11.95; dipropylene glycol 71.21; higher adducts 23.74; 6 The same 7 Glycols and cellosolve 8 same 9 same Propylene glycol 29.8; dipropylene glycol 58.89; tripropylene glycol and higher adducts 11.21; water 0.10. Ethylene glycol 8.1; ethyl cellosolve 0.1; ethyl carbitol 8.37; diethylene glycol 4.83; triethylene glycol ethyl ester 13.96; triethylene glycol 23.63; tetraethylene glycol 21.93; higher adducts 19.0; water 0.08 Ethylene glycol 0.98; ethyl cellosolve 0.02; ethylcarbitol 7.94; diethylene glycol 5.01; triethylene glycol ethyl ether 15.34; triethylene glycol 27.11; tetraethylene glycol 28.17; water 0.10 Ethylene glycol 13.50; ethyl cellosolve 1.50; ethyl carbitol 9.01; diethylene glycol 4.94; triethylene glycol ethyl ester 11.17; triethylene glycol 23.13; tetraethylene glycol 22.12; higher adducts 14.53; water 0.10. w ooh C - Experience Table 2 —-----------—--———————-------------------- --- Uploaded to experience ABSK technical bottoms arbitrariness states Total including --------- butyl cellulose ..... 1 "ROPI f jihkujivh alkylbenzenesulfo- sulfuric KIS ” paraffins Lozolva Langley and cellulose ACIDS LOTS butylcar Kolya, g SolBOB, - —— ------ bitola, g G g - 1 % ^g 1 g ^g 1 * 100 88.0 88.0 20 2.0 10.0 10.0 233 120 108.6 91.5 1.8 1,5 9.6 8.0 196 - 110 98.2 89.3 1.9 1.7 9.9 9.0 220 - 115 106.1 92.3 1.4 1,2 7.5 6.5 - 256.5 125 115.0 92.0 1.25 1,0 8.75 7.0 - ·. 187.5 130 117.26 88.5 1,04 0.8 11.7 10.7 - 390.0 125 111.95 89.15 2,3 1.85 1D75 8.6 - 275 125 115.0 92.0 1.25 1,0 8.75 7 * 0 - - 232,2 105 94.06 89.15 1.94 1.85 9.0 8.6 - • 210 115 106.1 92.3 1.40 1.20 7.5 6.5 - 207 - Continuation of the table. 2 Experience Uploaded Ratio of vat Tempelatura, ¹ ? FROM Received a solution of ABS CaO Ca (OH) ^ residues of ABSK, ppm Total IN including g g g ABSK water G g 1 13.8 2.33: 1 70-80 309.4 95.9 31,0 4.7 1,5 2 12.5 - 1.63: 1 70-80 291.1 110.6 38,0 4 3 1.3 3 11.5 2.0: 1 70-80 337.4 107.05 35,4 5,0 1,5 4 And 9 - 2.22: 1 70-80 350,0 107.8 30.8 3,5 1,0 5 12.7 - 1.5: 1 70-80 293.7 117.2 39.9 3.2 M 6 17.0 3 * 0: 1 70-80 479.5 119.5 25.0 6.5 1.4 7 11.9 2.2: 1 70-80 407.0 113.74 30.6 4.1 1,1 8 16.9 1.86: 1 70-80 334.8 116.8 34.9 '3.7 1,1 9 10.9 - 2: 1 70-80 320.9 102.5 36,2 4.3 1.4 10 11.9 1.71: 1 70-80 330.6 108.1 35.9 4.1 1.4 Continuation of the table. 2 I Experience -------——— Precipitate received The amount of products obtained, g Losses ΙΞΞ ί ί. ‘ 32,4 9.3 341.8 5,0 1.4 2 32,0 9.9 323.0 5.5 1.7 3 34.8 9,4 337.4 4.1 1,2 4 30,4 8.1 381.4 3.0 0.8 5 29.0 9.0 322.7 2,5 0.8 6 50,5 9.5 530.0 7.0 1.3 7 35.0 8.6 - 407.0 * 4.9 1,2 8 35,3 9.6 370.1 4.0 1,2 9 32,5 9.8 320.9 5,0 1,5 10 29.1 8.15 330.6 3.3 1,0 Table 3 Foaming mode The coefficient of foaming of a sample of vinyl leather Temperature, ’C Time s 1 PI ’1 4 ^s 4 ’G I ...; - 200 90 2,33 2.29 2.31 2.42 1.83 2.20 2.22 2.23 2.28 2.40 2.18 200 105 2.65 2, M 2.57 2.52 2.03 2.48 2.52 2.47 2.67 2.59 2.47 210 60 2.67 2.42 2.55 2.53 1.96 2.51 2.53 2.58 2.69 2.63 2.48 210 75 2.85 2.67 2.57 3.00 1.81 2.67 '2.57 2.73 2.76 2.90 2.67 220 fifty 2,37 2, A1 2.35 3.05 2.12 2.34 2.34 2; 39 2.39 3.00 2,31 220 60. 2.87 2.71 2.69 2.92 2.21 2.41 2.74 2.79 2.73 2.95 2.68