SU717096A1 - Carbochain polymer based composition - Google Patents

Description

one. .

This invention relates to the plastics industry, in particular, to the development of a stabilized team based on a carbon chain palimer.

A known composition based on a carboxylic polymer, comprising a phenolic stabilizer, for example, 2,4,6-tricumylphenol (TCP) 1 in an amount of, for example, 0.2 parts by weight. per 100 weight parts by- . Leamer. However, the known composition does not lead to sufficient stability of the polymer and has poor technological properties.

The purpose of the invention is to increase the stability of the polymer, to improve the technological; properties and sanitary conditions of its processing.

This goal is achieved by the fact that as a phenolic stabilizer the composition contains 2-methyl-4 6-di (a, and dimethylbenzyl) phenol in an amount of 0.2-3 parts by weight. per 100 weight parts polymer

The specified stabilizer is hereinafter designated BC-250.

- VS-250 is obtained by the arylalkylation method of aromatic hydrocarbons with unsaturated hydrocarbons.

The stabilizer BC-250 proposed for polymer compositions has several advantages:

The BC-250 stabilizer is non-staining, affordable and more effective.

The BC-250 stabilizer can be used both independently and in a mixture with hydrofluorine stabilizers from a number of amines, substituted phenols, phosphites and sulfur-containing compounds.

The stability of polymer compositions is assessed by the value of the index of the SIRS household value,%) by Wallace:.

SSP%) plasticity after aging .f.f plasticity before aging

and on the preservation of plasto-elastic properties under conditions of heat aging and thermomechanical treatment on rollers (150 ° C, 20 min),

Stability of polymer compositions in an oxygen atmosphere at a temperature of 760 mm RTL. the magnitude of the induction period of oxidation and the time of absorption by the polymer of 0.1 wt.% oxygen by weight are estimated. Stability is also evaluated by the degree of structuring of rubber samples by determining the content of helium, wt.%. The invention illustrates the examples. . I Getting stabilizers VS-250. Method A. Into a flask purged with nitrogen, 10 g of ortho-cresol, 0.27 g of aluminum in the form of shavings are loaded and gradually shredded in an oil bath to 185-187 ° C until the aluminum has completely dissolved. The reaction mass is cooled to 130 ° C and 260 g (2.1 g-mol dry alpha-methylstyrene is added at such a rate that the temperature of the reaction mass does not increase. The reaction mass is stirred at 130 + 5 ° C for 2 hours water, benzene, the organic layer is separated, dried, benzene is distilled off, and the residue is distilled in vacuo to give 275.2 g (80% of theoretical) 2-methyl-4; 6-di (a, a-dimethylbenzene-1ol) with a boiling point of 222-225 ° C (4 mm Hg). The product is a viscous, clear liquid that slowly crystallizes on standing. Poor cr istals with a melting point of 88-89 ° C from alcohol). Found molecular weight - 340.2, calculated - 344.5., Comparative years. Elementary analysis: found:, C - 87.0 H, - 8.4 calculated: C - 87.16 H - 8.19. Method B. Into a flask purged with nitrogen, 108 g (1 g-mol) of ortho-cresol, 10 g of orthbresol-aluminum are loaded, heated to 130 ° C and 260 g (2.1 g-mol) of dry alpha are added with stirring -methylstyrene at such a rate that the temperature of the reaction mass does not rise above 160 ° C. The reaction mass is stirred for 2 hours, cooled to 20 ° C, 350 ml of isopropyl alcohol is added, cooled and after separation 9993 g (87% of theoretical) 2-methyl-4, 6-di / a, O dimethylbenzylphenol are obtained, t. w1. 8788 C. After recrystallization from zanol, m.p. 88-89 ° C. The product is highly soluble in benzene, toluene, cyclohexane, poorly soluble in alcohols, hexane, insoluble in water, and not hydrolyzed. The product is non-toxic. According to the data obtained in the toxicology laboratory, it was not possible to establish a lethal dose in experimental animals. In tab. 1 shows the data on the volatility of BC-250 in comparison with ionol and neozone D. Volatility was determined using filter paper discs. T a b l and c a 1 angioxidants

kai can be seen from the table. 1 at elevated temperatures TbRT r1Shs, at which rubber mixtures are vulcanized and rubber extracted, BC-250 is much less volatile than ionol and Daozone D. (SKN-40) after the distillation of the monomers of the Shishgy stabilizer prepared by lio recheshu, g: Stabilizer Potassium rosin hydroxide Potassium hydroxide Water The dosage of the stabilizer BC-250 is 0.25, 0.7; 0.95%, TKF - 0.5 and 1.2% by weight of rubber. The obtained rubber samples are subjected to aging in a thermostat in an atmosphere of air at 120 ° C for 6 hours and control the change in stiffness according to GOST. In addition, the samples are heated in a thermostat in air at 150 ° C for 40 minutes and the Wallace plasticity retention index (ICP,%) and the gel content in methyl ethyl ketone (IEC) are determined. For comparison, a sample from a known mixture is prepared and tested. Test data gfeivedeny in table 2.

5717096

The properties of the compositions using the well-known and Ephedloseshugo C1 stabilizers

Stabilizer

Dosage wt.% (On aliased)

OD5

0.7

0.95

Umst0, 5 1.2 From the table. 2 it is clear that ppopyk VS-250 is superior to TKF in terms of the effectiveness of HIV staion vii {sti. In accordance with the condition of aging, rubber with antioxidant BC-250 is structured / tied less than in the presence of 1ZO TCF.S Example 2. To samples (40 g) of SKN-40 butadiene-nitrile rubber containing BC-250 are added on rollers 0, 2 g (0.5 wt.%), 0.4 g (10 wt.%) And 0.6 g (1 wt.%) Three onylphosphate (polygard NF). The resulting samples are subjected to heat aging in air.

Properties of the composition Stabilizer, its dosage, wt.% T „-i --.-. VS-250 I Poligard NF

0.5 1.0

1.5

0.5

table 2

Heat aging

150 ° C, 40 min

CO.%

gel content in

MEC%

85

37.4 software 14.0 110 10.5

32.5

104 122 24.4

Table 3

37.4 27.2

h

22.6 19.4

10.5 1.5 {phi 150 ° C for 40 min, with this being determined the content of the gel in methyl Lyl ketone. : In addition, 0.2 g (0.5 wt.%) And 0.4 g (1.0 wt.%) Of the half-pitch NF are added to SKN-40 butadiene-syringe rubber samples, prefixed with 1.2 wt. % TCF. ; 7 1 1 сравн comparisons are obtained and tested on раз section 1 of SKN-40 rubber in Example 1, containing 0.25% by weight, 0.95% by weight, BC-250 2% by weight / popigard, 1.2% by weight TKF and a sample similar to the industrial type of cossack SKN-40 with a neozone content of D 2.6% by weight. The results of extracts are given in tabl. The content of the gel in the IEC after heat aging (150 ° C, 40 min) Properties of the composition

From tab. 3, it can be seen that the addition of toligard to the BS-250 product leads to an increase in its stabilization of stress in terms of thermal aging. A mixture of BC-250 with yolgyrd is superior to a mixture of TCF with a polygard, neozone and a polygard of NF in terms of the effectiveness of the process of structuring the temperature and temperature. ,/five

Example Z. In butadiene-nitriant latex with a content of acrylic acid nitrile of 38 wt.% (SKN-40) in example 1, the properties of the compositions are introduced.

8. Continuation tabl-3

slurry stabilizer (VS-250, TKF) at the rate of 2 wt.% by weight of rubber.

The obtained rubber samples were subjected to aging in air at 150 ° C for 30.40 and $ 0. 1YYY and the gel content was determined.

For comparison, SKN-40 samples with 2 wt.% Of ionol, 2 wt.% Of TCP and 2 wt.% Of polygard are obtained and tested. The latter are introduced into rubber analogously to VS-250 and TKF according to example 1.

Test data are given in table. four.

Table 4 As can be seen from the obtained data, the product VS-250 is superior to TCP, ionol and polygard in the effectiveness of the stabilizing effect. Example 4. In example 1, samples of SKN-40 butadiene-nitrile rubber are obtained with a BC-250 content of 0.25%, 0.7%, 0.95% From the table. 5 that rubber stabilized with BC-250 has a lower tendency to structuring under conditions of thermomechanical treatment on rollers as compared to rubber filled with TCF and net D Example 5. Based on SKN-40 rubber samples obtained in Example 1 and With a mixture of 0.7 wt.% And 1 wt.% Of BC-250, 0.7, and 1.1 wt.% Of TKF, rubber compounds are prepared according to the recipe, weight. H. Kauchuk100 Stearin technical1,5 Whitewash zinc szhie, marks M-1 5,0

Properties of rubber, 7

Composition properties

0.43

0.67 0.23 0.59 JO and 3.0%, TKF 0.7%, 1.2% by weight, and a specimen similar to SKN-40 industrial rubber with a neozone content of D 2.6% by weight. Samples of rubbers subjected to thermomechanical processing on the rollers at 150 ° C for 20 minutes and. control the change in stiffness according to GOST. These tests are presented in Table. 5. Table 5 Kapgaks Soot of mark DG-100 Sulfur technical The obtained rubber mixtures vulcanize at 142 + 1 ° С for 60 minutes. The plates of vulcanizates with a thickness of 2.0 + 0.3 mm are subjected to heat aging in a thermostat at 100 ° C for 3, 5, 7, 10 days and the change in the physicomechanical parameters of the vulcanizates is determined (tensile strength at breakdown and relative elongation) . These tests are presented in Table. 6. Table 6

eleven

717096

Rubber properties

Zhshshmy T Foy Ysov Solvent. The resulting filmPerimer 6. In polybutadiene. poluynny ky shdvervvyut aging in the closet when using organolithic catapizato-1 (30 C.

 iS-iSSiSfcrwJ; -

Comparative effectiveness of antioxidants tipK aging; 12

Continuation of table 6

Table 7 As follows from the table, mixtures of BC-250 with phosphite and DLTPP are effective. Example 7. A styrene butadiene block copolymer containing 30% bound styrene (DST-30) is injected on a roll mill at a temperature of 80-85 ° C with a certain amount of antioxidant. In tab. 8 shows the data on the preservation of the turnover index (I.R.) of DST-30, charged with BC-250 based stabilizer mixtures.

Comparative effectiveness of antioxidants with sentenin DST-30 (aging time - 20 min)

one.

Ionox -330 (05) BC-250 (0)

2. 3. Ioiox-330 (0) DLTDP (0.5)

BC-250 (0.5) DLTDP (0.5)

BC-250 (0.5) polygard (0.5)

An example of low-density polyethylene is aging in an oxygen atmosphere with a grade of 15802-20 iio GOST 16337-70 at 40 pressure of 760 mm Hg. Art. and a temperature of 140 ° C. Melt stages are introduced with OD% BC-250, then the polypolymer is cooled as a control sample and Shenken ethylene filled with ionol (0.2 wt.%) is pressed from it. 0.2 mm thick and weighing 03QO g. Films under the test results are shown in Table 9.

Comparative effectiveness of antioxidants

Induction

Antioxidant period, min

256 48

BC-250 Joiol

Table 8

32.1 513

47.9 68.1 603

Table 9

Time for absorption of polymer by weight of 0.1% oxygen by weight, min

Claims (1)

300 65 A foreign antioxidant, 2,4,6-tris (4-hydroxy-3, 5-di-tertboupbenzyl) mesitylene known as ionox-330, which is currently used by a number of foreign companies instead of to stabilize block copolymers. As follows from the above data, BC250, as well as its mixtures (with dilapuril thiodipropionate DLTDP) or polygard, are more effective than analogous mixtures with ionox-330. is: As can be seen from the above, 1a 1x data of BC-2SO provides good stability of polyethylene to oxygen under aging conditions. Example 9. In a polystyrene with a molecular weight of 220 thousand, due to its polymerization, 0.2% by weight of BC-2SO was introduced in solution stages. The solvent is removed) 110t by injection. The polymer is crushed and aged in the atmosphere; oxygen P | temperature 150 ° C and oxygen extraction 760 mm hg As a control image; is polystyrene, protected by 0.2 wt.% iotol. For the control sample, the time to absorb 0.1% by weight of polymer by weight of oxygen is 100 minutes, with ionol-120, with BC-250 - 150 minutes. Thus, BC-250 is a good polystyrene antioxidant. As can be seen from Tables 1–9, Phase 1, the Fairy Stabilizer is lushping, providing one bit of carbon to the polymers, and improving the technical properties of the compositions. In addition, because of the low volatility of the stabilizer, the working conditions are improved. Formula of the invention Composition based on a carbon-chain polymer, which includes a perfusion stabilizer, which is based on the following: improvement of the processability and caHHtepmtx conditions of its processing, the composition contains as a phenolic stabilizer 2 - mixture 1-4, b-yes (abg-dimethylbeisyl) -feiol in the amount of 0.23 parts by weight on 10P weight.h. nonio a. ; Sources of information taken into account in the examination 1. USSR author's certificate N 260167 cl. C 08 L 9/00, 1970 (prototype).