RU2260020C1 - Method for preparing metal-containing lubricant for preparing materials made of chlorine-containing polymers - Google Patents

Abstract

FIELD: chemistry of polymers, chemical technology.

SUBSTANCE: invention relates to chlorine-containing polymeric composition that can be sued in manufacturing rigid, semi-rigid and soft materials. Method is carried out by interaction of alpha-branched saturated monocarboxylic acids of (C₁₀-C₂₈)-fraction with polyhydric alcohol at 180-230°C in the mole ratio = 1:(1-2) in the presence of metal oxides and their bi- and tri-component mixtures in the mass ratio MgO : CaO (or ZnO, BaO, CdO, PbO) = (0.25-1):(0.5-1) and MgO : CaO : ZnO (or BaO, CdO) = (0.5-1):(0.5-1), respectively, taken in the amount 0.5-2.0 wt.-% of the total reaction mass and without additional stages of neutralization, washing out, clearing and drying the prepared product. Ethylene glycol, glycerol, polyglycerol-vat residue after the glycerol distillation process can be used as a polyatomic alcohol. Invention provides preparing effective lubricants showing additional thermostabilizing capacity by ecologically safety technology, and expanding assortment of additives for polymeric articles also.

EFFECT: improved preparing method.

2 cl, 4 tbl, 32 ex

Description

The invention relates to the chemistry of polymers, in particular to chlorine-containing polymer compositions that can be used in the production of hard, semi-rigid and soft materials.

Known filled composition based on polyvinyl chloride, including a heat stabilizer, a filler is a modified calcium carbonate and a lubricant, which, in order to improve processability, contains calcium carbonate modified with 5-15 wt.% Polyvinyl chloride containing 0.08-0.12 wt.% terminal carboxyl groups, in the following ratio of components in the composition, parts by weight:

Polyvinyl chloride 100 Thermal stabilizer 3-5 Specified Filler 1-200 Grease 1-2

(A.S. USSR No. 1164246, class C 08 L 27/06, C 08 K 9/04, BI No. 24, 06/30/1985).

Closest to the claimed one is a polymer composition comprising polyvinyl chloride, a metal-containing thermal stabilizer and a lubricant, where triacetic glycerol ether (TU 6-05-05-317-85) is used as a lubricant, in the following ratio, wt.h .:

Polyvinyl chloride 100 Metal-containing thermal stabilizer 0.5-5.0 Triacetic glycerin ester 0.3-5.0

(AS USSR No. 2048494, class C 08 L 27/06, C 08 K 5/10, BI No. 32, 11/20/1995).

The authors conducted additional tests of the polymer composition based on polyvinyl chloride using triacetic glycerol ether as a lubricant and determined its effect on thermal stability and melt flow rate.

Thus, thermal stability at 185 ° C is 47 minutes, the melt flow rate at a temperature of 200 ° C and a load of 21.6 kgf is 2.1 g / 10 min.

The disadvantage of the polymer composition using triacetic glycerol ether as a lubricant is its low thermal stability and melt flow rate.

The objective of the invention is to obtain effective lubricants with additional thermostabilizing ability of environmentally friendly waste-free technology, as well as expanding the range of quality chemicals additives for polymer products.

This object is achieved in that metal-containing lubricants of chlorine-containing polymeric materials are obtained in one step by reacting alpha-branched saturated monocarboxylic acids of the C ₁₀ -C ₂₈ fraction with polyhydric alcohol at 180-230 ° C in a molar ratio of 1: (1-2) in the presence of metal oxides or their two- and three-component mixtures with a mass ratio of MgO: CaO or ZnO, BaO, CdO, PbO in a ratio of 0.25-1: 0.5-1 and MgO: CaO: ZnO or BaO, CdO in a ratio of 0, 5-1: 0.5-1: 0.5-1 in an amount of 0.5 -2.0 wt.% From the total reaction mass to an acid value of not more than 3 mg OH / g.

Additional stages of neutralization, washing, clarification are not required, since the reaction products are obtained immediately with a low acid number and a satisfactory color.

The presence in the reaction mass of divalent metal oxides or their bicomponent and ternary mixtures accelerates the interaction of alpha-branched saturated monocarboxylic acids with polyhydric alcohol, and they themselves form monocarboxylic acid salts, which in the future in polymer compositions act as thermostabilizer.

The presence of an ester group provides good compatibility with the polymer base of the composition.

An unexpected synergistic effect was obtained, which is expressed in the fact that in the syntheses in the presence of a two-component mixture of oxides, one of the components of which is magnesium oxide, the lubricants are lighter, transparent without sludge and with an increased value of the operational indicator - thermal stability.

As the polyhydric alcohol use: ethylene glycol, glycerin, polyglycerin - distillation residue of glycerol distillation (TU 6-01-0203314-92-89).

As alpha-branched saturated monocarboxylic acids, C ₁₀ -C ₂₈ acid fractions obtained by telomerization of ethylene with isobutyric or butyric acids in the presence of a radical initiator of ditretbutyl peroxide are used. (TU 2431-200-00203312-2000).

The invention is illustrated by the following examples.

Example 1. In a tank equipped with a stirrer, thermometer, Dean-Stark nozzle, a nozzle for purging nitrogen, alpha-branched saturated monocarboxylic acids (1 mol), glycerin (1 mol), zinc oxide (0.5 wt.% From the total reaction mass). Then, the reaction mixture is heated at atmospheric pressure, in a stream of nitrogen at 220 ° С with removal of the reaction water for 6.5 hours. The acid number of the obtained product is 2.6 mgKOH / g. Yield 95.2%.

Examples 2-32. The syntheses are carried out analogously to example 1, the composition of the reaction mixture, temperature, synthesis time, acid number, product yield are given in table. 1.

Metal-containing greases are colorless to light yellow fluids.

The effectiveness of the obtained metal-containing lubricants in relation to polymer compositions is evaluated as follows: the polymer is mixed with the components of the composition in the mixer, then films 0.4-0.5 mm thick are rolled from it and the “thermal stability” index is determined according to GOST 14041-91 and the melt flow rate is IIRT-1M device according to GOST 11645-73.

Similarly, tests were carried out using triacetic glycerol ether (prototype).

The composition of the polymer compositions and the test results are shown in table 2.

Using the proposed method for producing metal-containing lubricants for polymers will allow:

- increase the yield of target products;

- to simplify and reduce the cost of the process by eliminating the stages of neutralization, washing, drying, clarification and the formation of light products with a low acid number;

- carry out the process in environmental safety mode, without the formation of wastewater, by eliminating the stage of neutralization and washing the product from the remains of unreacted acid;

- expand the range of lubricants for polymer products with good compatibility with the polymer base of the compositions and increased thermal stability;

- to obtain light transparent products that provide high thermal stability of the polymer composition due to the content of magnesium oxide in two- and three-component mixtures of metal oxides.

Table 1 When measures
No. The composition of the reaction mixture Synthesis Conditions Acid number, mgKOH / g Exit, % The ratio of that: glycerin Metal oxide, content, wt.% (Of the total reaction mass) Temperature ° C Time h 1. 1: 1 ZnO 0.5 210 6.5 2.6 95.2 2. 1: 1 MgO 0.5 220 8 2,5 95.9 3. 1: 1,5 ZnO 1.0 210 7.0 2,3 96.4 4. 1: 1,2 ZnO 0.5 + CaO 0.5 190 7.0 2.0 96.3 5. 1: 1.3 PbO 1.0 + ZnO 0.5 230 7.5 2.9 97.0 6. 1: 1,2 MgO 0.75 + PbO 0.5 220 6.5 2,4 96.4 7. 1: 1,5 MgO 0.5 + ZnO 1.0 190 6.0 2.7 95.3 8. 1: 1,2 MgO 1.0 205 7.0 2.9 96.2 9. 1: 1.3 MgO 0.5 + BaO 0.5 230 7.5 1.8 97.3 10. 1: 1,1 MgO 0.75 + ZnO 0.25 220 6.5 2.0 98.0 eleven. 1: 1.4 MgO 0.5 + CaO 0.5 210 7.0 1.4 97.5 12. 1: 1.3 PbO 0.5 195 7.5 2.6 97.1 thirteen. 1: 1,2 MgO 0.5 + CdO 0.5 200 7.0 2,8 95.9 14. 1: 1.4 MgO 0.5+ CaO 0.5 + ZnO 0.5 205 7.5 2.6 98.2 fifteen. 1: 1,2 MgO 1.0 + ZnO 0.5 + BaO 0.5 195 7.0 2.7 98.0 16. 1: 1,1 MgO 0.5 + BaO 1.0 + CdO 0.5 210 6.5 2,4 97.9 to-that: ethylene glycol 17. 1: 2.0 ZnO 0.5 180 6.5 2,4 95.3 eighteen. 1: 2.0 MgO 0.25 + ZnO 0.5 185 6.0 3.0 95.2 19. 1: 2.0 PbO 0.8 190 8.0 2,8 96.1 20. 1: 2.0 CdO 0.25 + BaO 0.5 185 6.5 2,8 95.8 21. 1: 2.0 MgO 1.0 + CaO 0.5 185 7.5 2,8 96.4 22. 1: 2.0 MgO 0.5 + PbO 0.5 190 6.5 2,3 96.6 23. 1: 2.0 MgO 0.5 + CaO 0.5 + ZnO 0.5 185 7.0 2,3 97.2 24. 1: 2.0 MgO 0.5+ ZnO 0.5 + BaO 0.5 180 7.5 2,5 96.9 25. 1: 2.0 MgO 0.5 + BaO 1.0 + CdO 0.5 180 7.5 2,8 97.1 to-that: polyglycerols 26. 1: 2.0 ZnO 0.5 205 7.0 1.9 97.8 27. 1: 1,5 PbO 0.75 + MgO 0.5 220 8.0 2,4 97.0 28. 1: 2 MgO 0.5 + ZnO 0.5 200 6.0 2.9 96.8 29. 1: 1,5 ZnO 0.5 + PbO 0.5 210 6.5 2.9 96.8 thirty. 1: 2.0 MgO 0.5 + CaO 0.5 + ZnO 0.5 220 7.0 2,5 97.4 31. 1: 1,5 MgO 0.5 + ZnO 0.5 + BaO 0.5 200 7.0 2.9 98.7 32. 1: 2.0 MgO 0.5 + BaO 1.0 + CdO 0.5 200 7.5 2.6 98.0

table 2 Components Composition, parts by weight Polyvinyl chloride 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 Tribasic Lead Sulfate 3,5 3,5 3,5 3,5 3,5 3,5 3,5 3,5 3,5 3,5 3,5 3,5 3,5 3,5 3,5 3,5 3,5 Calcium sterate 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 Triacetic glycerol ether (prototype) 0.5 - - - - - - - - - - - - - - - - Metal-containing grease according to the examples of the table. 1. - - - - - - - - - - - - - - - - - 1 - 0.5 - - - - - - - - - - - - - - - 2 - - 0.5 - - - - - - - - - - - - - - 3 - - - 0.2 - - - - - - - - - - - - - 4 - - - - 0.75 - - - - - - - - - - - - 5 - - - - - 0.2 - - - - - - - - - - - 6 - - - - - - 1,5 - - - - - - - - - - 7 - - - - - - - 0.5 - - - - - - - - - 8 - - - - - - - - 0.2 - - - - - - - - nine - - - - - - - - - 0.75 - - - - - - - 10 - - - - - - - - - - 0.5 - - - - - - eleven - - - - - - - - - - - 0.75 - - - - - 12 - - - - - - - - - - - - 1,5 - - - - thirteen - - - - - - - - - - - - - 0.5 - - - 14 - - - - - - - - - - - - - - 0.75 - - fifteen - - - - - - - - - - - - - - - 0.2 - 16 - - - - - - - - - - - - - - - - 0.5 Melt flow rate, T = 200 ° C, P = 21.6 kgf, g / 10 min 2.1 4.0 4.3 3,7 4.8 3.9 6.1 4.6 4.1 5.2 4.8 5,4 6.4 5,0 5.8 4.0 4.6 Thermostability, T = 185 ° C 47 89 105 95 125 95 145 130 98 125 130 142 134 145 138 104 120

Table 3 Components Composition, parts by weight Polyvinyl chloride 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 Tribasic Lead Sulfate 3,5 3,5 3,5 3,5 3,5 3,5 3,5 3,5 3,5 3,5 3,5 3,5 3,5 3,5 3,5 3,5 Calcium sterate 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 Metal-containing grease according to the examples of table 1. - - - - - - - - - - - - - - - - 17 0.2 - - - - - - - - - - - - - - - eighteen - 0.5 - - - - - - - - - - - - - - 19 - - 0.2 - - - - - - - - - - - - - twenty - - - 0.75 - - - - - - - - - - - - 21 - - - - 0.2 - - - - - - - - - - - 22 - - - - - 1,5 - - - - - - - - - - 23 - - - - - - 0.5 - - - - - - - - - 24 - - - - - - - 0.5 - - - - - - - - 25 - - - - - - - - 0.2 - - - - - - - 26 - - - - - - - - - 0.5 - - - - - - 27 - - - - - - - - - - 0.75 - - - - - 28 - - - - - - - - - - - 1,5 - - - - 29th - - - - - - - - - - - - 0.5 - - - thirty - - - - - - - - - - - - - 0.75 - - 31 - - - - - - - - - - - - - - 0.2 - 32 - - - - - - - - - - - - - - - 0.5 Melt flow rate, T = 200 ° C, P = 21.6 kgf, g / 10 min 4.1 4.6 3,7 5,4 3.9 6.1 4.9 5.1 4.0 4.6 5,4 6.3 5,0 5.7 4.2 5.1 Thermostability, T = 185 ° C, min 85 115 95 125 96 145 132 137 142 100 128 139 125 140 131 150

Table 4 Components Composition, parts by weight Chlorinated polyvinyl chloride 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 Tribasic Lead Sulfate 3,5 3,5 3,5 3,5 3,5 3,5 3,5 3,5 3,5 3,5 3,5 3,5 3,5 3,5 3,5 3,5 Calcium sterate 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 Metal-containing grease according to the examples of table 1. - - - - - - - - - - - - - - - - 1 0.5 - - - - - - - - - - - - - - - 2 - 0.5 - - - - - - - - - - - - - - 6 - - 0.2 - - - - - - - - - - - - - 7 - - - 0.75 - - - - - - - - - - - - 8 - - - - 0.5 - - - - - - - - - - - thirteen - - - - - 1,5 - - - - - - - - - - fifteen - - - - - - 0.5 - - - - - - - - - 17 - - - - - - - 0.2 - - - - - - - - 19 - - - - - - - - 0.75 - - - - - - - 22 - - - - - - - - - 0.5 - - - - - - 23 - - - - - - - - - - 0.75 - - - - - 25 - - - - - - - - - - - 1,5 - - - - 26 - - - - - - - - - - - - 0.5 - - - 27 - - - - - - - - - - - - - 0.75 - - 28 - - - - - - - - - - - - - - 0.2 - 32 - - - - - - - - - - - - - - - 0.5 Melt flow rate, T = 200 ° C, P = 21.6 kgf, g / 10 min 2.9 3.2 3.3 4.1 3.6 5.1 4.2 3.0 4,5 4.2 4.7 5,4 3.9 4.6 3,1 4.1 Thermostability, T = 185 ° C 67 68 85 96 82 125 92 65 85 91 99 110 89 115 90 91

Claims (2)

1. The method of producing metal-containing lubricants for the production of materials from chlorine-containing polymers by the interaction of alpha-branched saturated monocarboxylic acids with polyhydric alcohol in the presence of a catalyst by heating and vigorous stirring with distillation of reaction water, characterized in that the process of interaction of alpha-branched saturated monocarboxylic acids fraction C ₁₀ -C ₂₈ with a polyhydric alcohol at 180-230 ° C in a molar ratio of 1: (1-2) is carried out in the presence of a catalyst - metal oxides or their two and three component mixtures in an amount of 0.5-2.0% of the total reaction mass to an acid value of not more than 3 mg KOH / g, without additional stages of neutralization, washing, clarification and drying of the resulting product. 2. The method according to claim 1, characterized in that CaO, CdO, BaO, PbO, ZnO, MgO and their two- and three-component mixtures are used as metal oxides at a mass ratio of MgO: CaO or ZnO, BaO, CdO, PbO in the ratio of 0.25-1: 0.5-1 and MgO: CaO: ZnO or BaO, CdO in the ratio of 0.5-1: 0.5-1: 0.5-1.