SU856390A3 - Rubber mixture based on natural rubber or combination of butadiene and butadienestyrene rubbers - Google Patents

Description

Bis {cyclohexylthio) phenylcarbamic acid 1,3-phenyl ester

Bis (isopropylthio) phenylcarbamic acid 1,3-phenyl ester; (4-methyl-1,3-phenylene) -bis- {cyclohexylthio) -carbamic acid dimethyl ester;

methylenebis- (1,4-phenylene) -bis- (cyclohexylthio) | -carbamic acid dimethyl ester;

(4-methyl-1,3-phenylene) -bis- (cyclohexylthio) -carbamic acid diphenyl ester;

(4-methyl-1,3-phenyl) -bis- (phenylthio) -carbamic acid diphenyl ester;

Si, s-bis (1,1-dimethyl ethyl) ester (4-methyl-1, 3-phenylene) bis (cyclohexylthio) -carbamothioic acid;

S S-bis- (1, 1-dimethioethyl) ether methylene bis; (1,4-phenylene) -bis- (cyclohexylthio) -carbamothioacid;

Bis (cyclohexylthio) phenylcarbamic acid 1,2-phenylene ester ;:

1,4- Phenylene ester of bis- (cyclohexylthio) -phenylcarbamic acid

1, 4-phenylene ester of (phenylthio) -phenylcarbamic acid;

(Phenylthio) phenylcarbamic acid 1,2-phenylene ester;

1,4- Phenylene ester of bis (phenylthio) phenylcarbamic acid;

butane-1,1-diyl-di- 2- (1,1-dimethylLethyl) -5-methyl-1, 4-phenylene-bis- (cyclohexylthio) -phenylcarbamic ester. acid, with a ratio of components, parts:

Natural rubber or a combination of butadiene and styrene-butadiene rubbers in a ratio of 35: 89100 Sulfur 2-2.5 N- (tertiary butyl) -2-benzothiazole sulfenamide 0.5-2 Carbon black 45-67 Zinc oxide 3 Stearic acid 1-2 Oil 5 -15 Specified inhibitor of premature volc. Privizatsy, 5

Example 1. To a slurry of methyl ester of i-triphenylcarbamic acid (0.2 M) in 250 ml of heptane, a solution of 1,2-ethanedisulfenyl chloride (0.1 m) is added dropwise in 25 minutes. The reaction mixture is stirred for another 35 minutes, followed by filtration. The solid residue on the filter is washed with heptay, then sludge is prepared from it and water. The solid fraction of the product is obtained by filtration and. sushi ki on the air. The filtrate of the reaction mixture is washed with water and dried with sodium sulfate, heptane is removed by vacuum distillation. The remainder of the

is the second product fraction. The first and second fractions are combined, of which ethyl ether is prepared sludge, followed by filtration and air drying. 22.6 g of 1,2-ethanediylbis (thio) bisphenylcarbamic acid dimethyl ester with m.p. 147-148 ,. Chemical analysis yields 16.50% sulfur, compared with 16.34% calculated for,.

Example 2. Cyclohexanesulfenyl chloride (0.2 m) in a solution, in heptane, is added over 45 minutes at 24-26 ° C to a stirred sludge consisting of 34.6 g (0.1 M) S 5-1, Bisphenylcarbamothioacid 3-propanediyl ester, 20.4 g of triethylamine and 200 ml of heptane. After stirring for an additional 45 minutes, 200 ml of water are added. The reaction mixture is filtered to remove unreacted ether. The heptane layer of the filtrate is washed twice with water and dried with sodium sulfate, followed by removal of heptane by vacuum distillation. IR spectroscopy shows that the partially solidified residue is the product below. From the crude product and ethyl ether, sludge is prepared, which is filtered and air dried. S-, S-1,3-propanediyl bis- (cyclohexylthio) -phenylcarbamothioacid with m.p. 98-98.5 ° C. Analysis gives 22.38% sulfur compared to 22.31% calculated for CjgHjgN O i S ..

Example 3. Beneolsulfenyl chloride (0.2 M) in toluene is added for approximately one hour with a stirred sludge consisting of 34.8 g (0.1 M) of bisphenylcarbamic acid 1,3-phenylene ester, 22 g of triethylamine and 200 ml of toluene. The mixture is filtered to remove the by-salt. The filtrate is washed with water and dried with sulphate and atrium, resulting in the removal of toluene by vacuum distillation to obtain 58 g of a solid, crude product. The crude product is washed with hexane, filtered and air dried. After recrystallization from toluene, 42.1 g of bis (phenylthio) phenylcarbamic acid 1,3-phenylene ester are obtained. 121 ,. The analysis yields 11.20% sulfur as compared to 11.33% sulfur calculated for 0. Na O Sa Example 4. A solution of cyclohex nsulphenyl chloride (0.2 M) in that® luol is added to a slurry consisting of 36.5 g (0.1 M) of 4-methyl-1,3-phenylene-biscarbamic acid diphenyl ether, 22 g of triztylamine and 200 ml of toluene. After

 stirring the reaction mixture

within about 90 minutes, the side salt is removed by filtration. The filtrate is subjected to vacuum distillation to remove toluene. The residue is dissolved in ether, washed with water and dried with sodium sulfate. The ether is removed by evaporation, after which a gummy mass is obtained. A mass of varits in ether, resulting in a solid white precipitate. The precipitate is filtered off. (4-methyl-1,3-phenylene) -bis- (cyclohexylthio) -carbamic acid diphenyl ester is obtained with m.p. . Analysis yields 11.22% sulfur compared to 10.83% sulfur calculated for Cjj.

Other compounds (Examples 5-19) prepared in a similar manner are listed in Table 1. The intermediate in Example 15 is obtained by the interaction between phenyl isocyanate and 4, 4-butididenbis- (6-tertiary-butyl- / 4-cresol). The properties of N-sulfenyl derivatives of carbamic acid diester are listed in Table 1.

Table 1

5SflS-bis- (1,1-Dimethylethyl) ether (4-methyl-1,3-phenylene) -bis- (cyclohexylthio) -carbamothioacid Sl, 2-Ethanediyl ester of bis-, - (cyclohexylthio) -phenylcarbamotioc 1 slot 7S s -bis- (1,1-dimethylethyl) ether methylenebis- (1,4-phenylene) -bis- (cyclohexylthio) -carbamothioxides. 1, 2-ethanediyl bis (thio) bisphenylcarbamic acid 8-diphenyl ester (4-methyL-1, 3-phenylene) bis (cyclohexylthio) -carbamic acid 4 dimethyl ester 10 Methyl ibis (1,4-phenylene) bis-ester (cyclohexylthio) -carbamic acid 111,3-Phenylene ester of bis- (cyclehexylthio) -phenylcarbamic acid 121,3-Phenyl ester of bis- (isopropylthio) -phenylcarbamic acid 13Diphenyl ester of (4-methyl-1,3-phenylene) -bis- (Phenylthio) -carbamic acid 141,2-Phenylene ester of bis- (cyclohexylthio) -phenyl-carbamic acid 15Butane-1,1-diyl-di-G2- (1,1-dimvty et l) -5-methyl-1,4-phenylene ether bis- (cyclohexylthio) -phenylcarboxylic acid 161.4-phenylene ether bis- (cyclohexylthio) -phenyl carbamic acid 137-138 21.63 21.40 106.5-107 22.87 137-138 19.46 161 12.4.1 Resinous resin Resinous resin Resinous solid 11.85 124-125 12.91 123.5-124 11.08 Resinous solid 11.12 Resinous solid 7, 55 162-163 11,12 Liquid chromatography shows a mono-cyclohexylthio derivative. liquid chromatography shows a mono-phenylthio derivative. Liquid chromatography shows 17% mono-phenylthioproduct

,. EXAMPLE 20. In the proposed method, the following natures are applied.

Oily styrene butadiene rubber 1712

cis-4-polybutadiene rubber

Carbon black Zinc oxide Stearic acid

Rubber filling oil.

Paraffin

N - (1, 3-Dimethylbutyl) - (phenyl) -p-phenylenediamine

Sulfur

N- (T-butyl) -2-benz thiazolsulfenamide

Continued table. one

Rally and synthetic rubber mixtures (data are given in table 2).

table 2

100

89 35

7

3-. l

15 2

2 2,0

1.2 217.2 presence of less quantity presence of less quantity approximately

Mixtures containing no inhibitors are taken as controls. The amount of inhibitor is contained in other parts of the masterbatch. Properties rubber rubber compounds based on natural rubber

Rubber compounds based on synthetic rubbers

Dimethyl ester of 1 2-ethanediyl bis (thio) bisphenylcarbamic acid

1,2-ethanediylbis (thio) bisphenylcarbamic acid diphenyl ester

S S-1,2-Ethanediyl ester of bis- (cyclohexylthio) phenylcarbamothioacid

S sl, 3-Propandia-. Lovy ester- bis- (cyclohexylthio) -phenylcarbamothioic acid

1,2-ethanediylbis (thio) bisphenylcarbamic acid dimethyl ester Determination of Mooney viscosity at an average temperature of 121 ° C tg, minutes 27.9 53, Increase the deceleration of premature vulcanization,% Determination of the Mooney viscosity at an average temperature tj, minutes Increasing the slowing down of premature vulcanization% Tensile test at cf. 153с ЪОО MP (voltage at 300% stretch 11, 5 11, nor) UTS MPa (tensile strength) 28.9 29 570 580 Elongation,%

Fabricable compositions are determined by conventional methods as described above. The compositions and properties of rubber compounds are given in Table 3-12.

160

160

160 217, 2 217.2

0.3

0.3

0.3 0, 5 93 4.1 38.4 38.4 38 38 58 23.0 35.8 56 11.6 11.4 11.7 8.6 9.0 28.8 28.8 20.2 20.2 560 540 570 570 570

Rubber blends based on natural rubber Bis (phenylthis) phenylcarbamic acid 1,3-phenylene ester Bis (cyclohexylthio) phenylcarbamic acid 1,3-phenylene ester rubber

Bis (ieopropylthio) -phenylcarbamic acid 1,3-phenylene ester: Resin mixtures based on natural rubber Dimethyl ester (4-me; Thyl-1, 3-phenylene) -bis- (cyclohexylthio) -carbam of new acid Dimethyl methylene bis- (1,4-Phenylene) bis-. {Cyclohexylthio) -carbamic acid Diphenyl ester I-methyl-1, 3-phenylene) -bis- (cyclohexylthio) -carbamic acid Diphenyl ether (4-methyl-, 3-phenylene) - bis (phenylthio) -carbamic acid

Table 5

160

160

160

0.3

0.3

0.3

The compositions

S S-bis-fl, 1-dimethylethyl) ether (4-methyl-1, 3-phenyl) -bis- (cyclohexylthio) -carbamothio ACIDS

S S-bis- (1,1-Dimethylethyl) -ether methylenebis- (1,4-phenylene) -bis- (cyclohexylthio) -carbon of thioacid Definition of viscosity fio Flour at an average temperature of 121 ° C tj, 36.1 60.9 47, 4 minutes Increased slowing of premature vulcanization,% Tensile test with medium. temperature 153 ° С 10.8 11.5 11.7 29.4 30 29.1 UTS, MPa 600 610 590 Elongation,%

Rubber blends based on natural rubber

Bis (cyclohexylthio) -phenylcarbamic acid 1,2-phenylene ester; Bis (cyclohexylthio) -hechylcarbamic acid 1,2-phenylene ester

1,4-Phenylene ester of (phenylthio) -phenylcarbamic acid

1,2-Phenylene ester of (fe yltno) phenylcarbamic acid

1,4-Phenylene ester of bis- (phenylthio) -phenylcarbamic acid

Continued table. 7

. Mixes VW-TG - 11-GT-1--5YYY-YY-GT-G

0.3

6.3

: T a b persons a 9

156

1.60

0.3

: 0.3

0.3

0.3

0.3 31.5 57.2 50.7 27.9 40.2 40.9 44 47 12.1 9.8 11.5 11.7 11.9 2 & 7 28.5 28.9 28, 4 28.7 600 570 540 560 560 Properties Mooney viscosity determination at an average temperature tg, 31.5 51, minutes Increased retardation of premature vulcanization,% Tensile test at an average temperature of 1530 s MPa 12.1 y, 9 28.7 29.1 UTS, MPa Elongation,% 560,620

Table 11

Rubber blends based on natural rubber

Butane-1,1-diyl-di 2- (1,1-dimethylethyl) -5-methyl-1,4-phenylene ester of bHC- (cyclohexylthio) -phenylcarbamic acid

Table 12

Mixes, No.

Properties

Mooney viscosity determination at average temperature tj, minutes

Increasing the slowdown of premature vulcanization,%

Tensile test at medium temperature

Table 10 Mixes

The rubber mixture (Table 3,4) is the control, it is a natural rubber without an inhibitor, while the rubber mixture 6, also serving as a control, is a synthetic rubber without an inhibitor. The rubber mixtures 2,3 and 7 show that alkylene-bis- (tis) -bisphenylcarbamic acid esters are effective inhibitors of premature vulcanization. A comparison of the data for mixtures 2 and 5 3 shows that dimethyl ether is more effective than diphenyl ether. Mixtures 4 and 5 indicate the inhibitory activity of S S alkanediyl esters of bis- (cyclohexylthio) -phenylcarbamothioacid.

The inhibitory activity of 1,3-phenylene ester-B (thio) -phenylcarbamic acids is given in Table. 5.6. The data show that the isopropylthiol compound is twice as effective as the corresponding phenylthiol compound.

The compounds of the proposed method, derived from the esters of biscarbamic or biscarbamothioic acids, are listed as effective inhibitors in that bl. 8,9.

The inhibitory activity of phenyl esters of bisphenylcarbamic acids is shown in Table 5. The data show that the two thio substituents improve the inhibitory activity (see rubber blends 4 and 6).

The inhibitory activity of the compound obtained in Example 15 is given in Table. 11.12. The data show that 0.3 h. Inhibitor increases the inhibition of premature vulcanization by 45%.

Claims (1)

Invention Formula Rubber mixture based on natural rubber or a mixture of rubber-. 53.5 41.5 38.5 47.5 32 22 9.3 8.8 9.4 9.2 26.1 27.0 28.2 27.7 580 620 630 640 New and styrene-butadiene rubbers, including sulfur, vulcanization accelerator -N- {tertiary-butyl) -2-benzothiazole sulphenamide and a scorching derivative of carbamic acid, carbon black, zinc oxide, stearic acid and oil, differing from that of carbon dioxide increase the resistance to premature vulcanization, the mixture contains as an inhibitor of premature vulcanization the N-sulfenyl derivative of a carbamic acid diester selected from the group: 1,2-ethanediylbis (thio) bisphenylcarby1minoic acid dimethyl ester; 1,. 2-ethanediylbis (thio) bisphenylcarbamic acid diphenyl ester; S-l, 2-ethanediyl ester of bis- (cyclohexylthio) -phenylcarbamothio acid; , Bis- (cyclohexylthio) phenylcarbamothioacid 3-propanediyl ester; 1,2-ethanediylbis (thio) bisphenylcarbamic acid dimethyl ester; Bis (phenylthio) phenylcarbamic acid 1,3-phenyl ester; 1,3-phenyl ester. Bis- {cyclohexylthio) -phenylcarbaminoic acid; Bis (isopropylthio) phenylcarbamic acid 1,3-phenyl ester; (4-methyl-1,3-phenylene) -bis- (cyclohexylthio) -carbamic acid dimethyl ester; methylenebis- (1,4-phenylene) -bis- (cyclohexylthio) -carbamic acid dimethyl ester; . ; (4-methyl-1,3-phenylene) -bis- (cyclohexylthio) -carbamic acid diphenyl ester; (4-methyl-1,3-phenylene) -bis- (phenylthio) -carbamic acid diphenyl ester; S (1,1-Dimethyl ethyl) -. -ether- (4-methyl-1,3-phenylene) -bis- (cyclohexylthio) -carbamothioacid; S, S-bis- (1,1-dimethylethyl) ether of 1-methylenebis- (1,4-phenylene) -bis- (cyclohexylthio) -carbamothioic acid; Bis (cyclohexylthio) phenylcarbamic acid 1,2-phenylene ester; 1,4- Phenylene ester of bis- (cyclohexylthio) -phenylenecarbamic acid; 0 (Phenylthio) phenylcarbamic acid 1,4-phenylene ester; (Phenylthio) phenylcarbamic acid 1,2-phenylene ester; 1,4- Phenylene bis (phenyl 5 thio) phenylcarbamic acid ester; Butane-1,1-diyl di 2- (1,1-dimethylethyl) -5-methyl-1,4-phenylene 3 Bis (cyclohexylthio) phenylcarbamic acid ester, with a ratio of components, parts by weight: Natural rubber or a combination of butadiene and styrene-butadiene rubber in a ratio of respectively 35:89 100 Sulfur 2-2.5 Zinc Oxide3 N- (tertiary butyl) -2-benzothiazole; sulfenamide; 0.5-2 carbon black 45-67; Specified inhibitor of premature vulcanization; 0.3-0.5 5 Stearic acid 1-2 Oil. 5-15 Sources of information taken into account during the examination 1. Japan patent No. 49-14533, cl. 25 (f) IN, pub. 1974 (prototype).