DD299187A5 - Process for the preparation of sulfur-containing organosilicon compounds - Google Patents

Abstract

The invention relates to a process for the preparation of sulfur-containing organosilicon compounds which are used as silane coupling agents and as reinforcing additives in silicate-filled rubber compounds. The object of the invention is a simplified process in which neither increased pressure nor sulfidation agents or catalysts are required. According to the invention, an organosilane or organosiloxane of the general formula {organosilicon compound, sulfur-containing; silane coupling agent; Verstaerkungsadditiv; Rubber compound, silicate filled; organosilanes; organosiloxanes}

Description

in which

A = alkenyl, cycloalkenyl, cycloalkenylalkyl, alkenylaryl,

R ¹ to R ⁵ = each independently OR, A, alkyl, cycloalkyl, aryl,

R = A, alkyl, cycloalkyl, aryl and

η = 1 to 10

and with a boiling point of at least 460K, with sulfur or a mixture of hydrogen sulfide and sulfur in the molar ratios A: sulfur or hydrogen sulfide = 1: 1 to 1: 5 is reacted directly at temperatures above 420K.

2. The method according to claim 1, characterized in that the reaction takes place in the temperature range of 420 to 500 K.

3. The method according to claims 1 and 2, characterized in that when adding a mixture of hydrogen sulfide and sulfur, the mass fraction of sulfur in the range of 10 ~ ² to 10 ~ ¹ kg / kg based on silane or siloxane used.

Field of application of the invention

The invention relates to a novel simple process for the preparation of sulfur-containing organosilicon compounds. They are useful as silane coupling agents or as reinforcing additives in silicate-filled rubber compounds, including treads and carcasses. of vehicle tires, usable. In addition, sulfur-containing silane cement can! in the production of sealants, casting molds for metal casting, color and protective coatings, adhesives, asphalt mixtures and silicate-filled plastics. Finally, there are applications in the fixation of functional groups and drugs on inorganic carriers, eg. 8. in the immobilization of enzymes, in the production of fixed bed catalyst and in liquid chromatography.

Characteristic of the known state of the art

The preparation of sulfur-containing organosilicon compounds is possible by various methods. Thus, bisforgano-organooxysilyDigigosulfide, preferably bis (alkyl-organooxysilyl) oligosulfides or mercaptoalkylalkoxysilanes by reaction of Halogenalkyltrialkoxysilanen, in particular of Halogenpropyltrialkoxysilanen and Met ₂ S _x or MetSH (Met = NH ₄ , Na, K; χ = 1 to 6 ) (DE 2141159, DE 2212239, US 3978103, US 4048206).

The polysulfide Met ₂ S _x can also be generated in situ from MetOR (R = alkyl, cycloalkyl), MetSH and S'fDE 2542534, DE 2712966, DE 3311340).

Furthermore, the preparation of bis [(ß-trialkoxysilylethyl) benzyl] oligosulfides by reaction of ß-Trialkoxysilylethylbenzylhalogeniden with NaHS and S known (DE 3504241). The reaction of haloalkylalkoxysilane with S and H ₂ S in the presence of an amine or NH ₃ of alkoxysilylalkyl polysulfides has also been described (DE 2648241).

Furthermore, mercaptoalkylalkoxysilanes, preferably mercaptopropylalkoxysilanes, are converted into bisorganoorganooxysilyldigigosulfides, preferably to give bis (propyl-organooxysilyl) oligosulfides. According to DE 2141160, S ₁ HaI ₂ (z = 1 to 3, Hai = Cl, Br) or according to DE 2405758 sulfur is used for this purpose.

In the cited methods, it is disadvantageous that special Sulfidierungsagenzien, z. B. poly or hydrogen sulfides or sulfur halides are needed. In addition, undesirable reaction products such as metal halides or hydrogen halides, which must be separated in an additional process stage. The use of mercaptosilanes requires a prior, additional, expensive process stage.

The mentioned disadvantages are eliminated in the reaction of vinylsilanes with S or a mixture of S and H ₂ S to bis (-silylethyD-oligosulfides according to DE 2856229. The carried out at 100 to 200 ° C reaction, however, only when working under elevated pressure and in the presence of a sulphidation catalyst to the desired products.

Object of the invention

The aim of the invention is a process for the preparation of sulfur-containing organosilicon compounds which can be carried out without the use of pressure and without the use of special sulphidation agents or sulphidation catalysts.

Explanation of the essence of the invention

The invention had the object of developing a technically easily feasible process, starting from accessible starting materials for the production of sulfur-containing organosilicon compounds. The compounds produced should be usable as silane coupling agents or as reinforcing additives in silicate-filled rubber compounds

According to the invention the object is achieved in that an organosilane or organosiloxane of the general formula

A-ShR ² or Α-

A = alkenyl, cycloalkenyl, cycloalkenylalkyl, alkenylaryl,

R ¹ to R ⁵ = each independently OR, A, alkyl, cycloalkyl, aryl,

R = A, alkyl, cycloalkyl, aryl and

.1 = 1 to 10

and is directly reacted with a boiling point of at least 460K, with sulfur or a mixture of hydrogen sulphide and sulfur. The reaction takes place in molar ratios AiSchwefel or hydrogen sulfide = 1: 1 to 1: 5, at atmospheric pressure and temperatures above 420K. The temperature range is preferably from 420 to 500K. When using a mixture of hydrogen sulfide and sulfur, the mass fraction of sulfur is preferably between 10 ~ ² to Ό "'kg / kg.

The sulfur-containing organosilicon compounds prepared according to the invention are obtained as clear, oily, yellow to deep red-colored liquids. They are in dry, organic solvents, eg. As ethanol or Ν, Ν-dimethylformamide in any ratio undecomposed soluble. Without subsequent cleaning operations, they can be used immediately for all applications. Due to their high sulfur content or a large number of potential linkages in the molecule they are excellent Silanhaftmitte! or reinforcing additives in silicate-filled rubber compounds.

Surprisingly, according to the invention, it has been possible to prepare sulfur-containing organosilicon compounds without increased pressure and without the use of sulphidation agents or catalysts.

embodiments

In a 250 ml three-necked flask equipped with stirrer, internal thermometer and drying tube, organosilanes or organosiloxanes and sulfur powder are reacted at 450 to 480K. After the reaction time, the sulfur has completely dissolved. The reaction product is a clear, oily, colored liquid that is undecomposed soluble in dry organic solvents such as ethanol or N, N-dimethylformamide in any ratio.

The starting materials, reaction times and parameters of the reaction products are set forth in Examples 1 to 23 in Table 1.

Example 24

120 g (0.44 mol) of 4 (2-triethoxysilyl-ethylcycloxene and 4 g (0.12 mol) of sulfur powder are initially introduced into a 250 ml three-necked beaker with stirrer, internal thermometer, drying tube and gas inlet 301 (1.32 mol) of dry and HCl-free hydrogen sulphide are introduced as the reaction product, a yellow-green, in dry organic solvents, such as ethanol or Ν, Ν-dimethylformamide, undecomposed soluble in any ratio, clear, oily liquid Yield is 158 g (92.9% of theory) The elemental analysis gave the following mass fractions in 10 ~ ² kg / kg:

Found .: C 42.83 H 7.57 S 24.57

calc .: C 42.61 H 7.65 S 25.09

Table 1

Ex. Organo-organo raw materials [minor sulfur [Mol] reak No. silane or siloxane 0.367 (gl 0.367 tion time 4 (2-triethoxysilylethyl) Ig) 11.8 0.734 [H] 1 cyclohexen 100 23.5 1.1 0.5 2 35.3 1.468 1.0 3 47,07 1,835 1.5 4 0.337 58.84 0.674 3.0 5 21.6 1,011 5.0 6 Exo-8 and R :: o-9-triethoxysilyl 100 32.4 1.0 7 endotricyclo- 1,348 2.5 (5,2,1,0 ²⁶ | dec-3-en 0.312 43.3 0.624 8th 5-Triethoxysilylbicyclo 20 4.0 9 [2,2,1] hept-2-ene 80 0.936 2.0 30 1,248 10 40 3.5 11 5.0

Table 1 (continued)

5-diethoxymethylsilylbicyclo [2,2,1] hept-2-one

80

1,060

3.5

(Trimethoxyethoxy) vinylsilane

80

18.3 0.57 4.0 27.4 0.855 6.0 36.5 1.14 8.0

1,3-divinyl-1,1,3,3-tetraethoxydi-80,261

siloxane

0.522

0.783

2.0

4.0

Diethoxy (phenyl) vinylsilane

80

23.1 0.72 2.0 34, C 1,079 4.0 46.2 1.44 6.0 22.3 0.694 3.0 33.4 1,041 6.0 44.5 1,3.38 9.0

Mixture of 4-triethoxysilylcyclopent-1-ene and 3-triethoxysilyl-cyclopent-1-ene

80

Table 1 (continued) Reaction products

Yield analysis data [10 ² kg / kg]

C [% d.Th.] Gef. ber. gef.

calc.

gef.

calc.

colour

97.9 98.0 96.8 95.2 95.1

98.3 97.4 97.7

54.89 48.31 45.71 41.15 32.32

55.22 48.96 45.6! 41 / Ju 32,85

9,10 8,21 7,46 7,40 5,25

9.27 8.38 7.65 7.04 5.52

10,23 19,01 26,07 30,73 36,82

10.5

19.05

26,09

32,00

37.04

53.48 48.64 43.67

53.29 48.94 45.24

7.76 7.03 6.05

7,83 7,19 6,64

16,83 23,37 28,13

17.78 24.50 30.20

yellow

yellow-orange

golb Orange

orange

red

yellow-green orange red

9 10 11 98.3 97.45 95.42 48.83 43.83 38.74 48.71 44.28 40.59 7.51 6.78 6.08 7.55 6.86 6.29 19,40 25,93 31,25 20,0 27,28 33,34 yellow-green orange red 12 97.1 44.27 44.68 6.81 6.87 28.91 29.82 Orange red 13 14 15 91.7 92.3 90.2 37.79 34.97 31.63 38.35 35.08 32.33 6.83 5.96 5.64 7.02 6.42 5.92 15,23 22,41 27,31 18.61 25.54 31.38 yellow orange red 16 17 97.8 96.3 38.51 35.27 38.89 35.74 6.98 6.44 7.07 6.51 17,12 22,73 17,3 23,89 red deep red 18 19 20 93.4 91.3 90.8 49.53 44.12 39.82 50.31 45.25 41.11 6.24 5.63 5.08 6.33 0.70 5.17 20,86 28,61 33,71 22.38 30.2 36.58 orange red red deep red 21 22 23 93.4 90.2 88.6 44,23 39,37 34,39 44.86 40.46 36.84 7.46 6.52 6.01 7.53 6.79 6.18 20.08 26.71 31.85 21.77 29.45 35.76 orange red red deep red

example

Analogously to Example 24 with the following modifications:

- Template: 100 g (0.337 mol) of 3-triethoxysilyltricyclo (5.2.1.0 ²⁶ | dec-8-enund4g (0.12 mol) of sulfur powder

- Introduction of 1.21 (0.675 mol) of hydrogen sulfide

- Reaction time: 1.5h

Yield: 121 g (95.0% of theory)

- Elemental analysis:

Found: C 53.24 H8,? 7 S 17.41 calc .: C53.00 H 8.34 S 17.68

The S-containing silanes according to the invention are particularly suitable as adhesion promoters or reinforcing additives for rubber mixtures based on natural or synthetic rubbers or mixtures thereof containing as fillers silicate fillers and optionally carbon black and sulfur and, inter alia, conventional accelerator systems. Here are the term "siliceous fillers" to rubber compatible and in rubber mixtures einarb'.luar bright fillers consisting of silicates containing Silikr.te or contain silicates chemically bound to understand .. In particular, these bright fillers, natural, fumed or precipitated silicas and synthetic or naturally occurring silicates.

The aforementioned silicallllllstoffe are preferably in amounts of 1 to 20CpHR (parts by weight per 100 parts by weight

Rubber) used.

The silanes according to the invention were tested for their effectiveness as adhesion promoters in various rubber mixtures of the following composition, in each case against a corresponding O-blend without added silane. (Details of quantities in parts by weight):

Recipe A total comparison Inventive mixtures 1712) 003 004 005 > 006 SBR recipe Recipe B mixture OeSBR / BR recipe 001 002 100 100 100 100 Styrene-butadiene 100 100 10 10 10 10 Rubber (TypeSB152H) 5 ö 5 5 aromatic 10 10 2 2 2 2 processing oil 5 5 1 1 1 1 zinc oxide 2 2 2 2 2 2 stearic acid 1 1 Ozone protection wax 5 2 1.5 1.5 1.5 1.5 chalk N-cyclohexyl-2-benzo- 1.5 1.5 erf indunnsgemäßes silane according to Preparation Example 4 0.3 0.3 0.3 0.3 thiazyl-sulfenamide total 2.5 2.5 2.5 2.5 Tetramethylthiuramdi- 0.3 0.3 40 40 40 40 sulfirl 2.5 2.5 sulfur 40 40 precipitated silica - - - - erfindungsgemp.ßesSilan 3 - - - according to manufacturing - 3 - 3 - - example 1 - - _ _ 3 _ 2 - - - - - 3 3 _ _ 167.3 167.3 167.3 167.3 4 _ - 5 167.3 167.3 comparison Verglt'chs- Fiction mixture mixture contemporary Year-soot mixture 001 002 003 110 OD 110.00 110.00 20.00 20.00 20.00 oil-extended styrenebutadiene rubber (type SBR 70,00 40,00 40,00 1,4-cis-polybutadiene - 30.00 30.00 HAF carbon black (TypeP324) 7.50 7.50 7.50 precipitated silica 3.00 3.00 3.00 aromatic processing oil 1.00 1.00 1.00 zinc oxide 1.50 1.50 1.50 stearic acid 1.50 1.50 1.50 N-phenyl-2-naphthylamine 2.00 2.00 2.00 1.50 1.50 1.50 2.50 2.50 2.50 - - 3.00 220.50 220.50 223.50 N-phenyl-N'-isopropyl-p-phenylenediamine Ozone protection wax N-cyclohexyl-2-benzothiazyl-sulfenamide sulfur

Recipe C EPDM recipe

-5- 299 187 Veigleichs- invention mixture mixture 001 002 75.00 75.00 25,00 25,00 40,00 40,00 50,00 50,00 50,00 50,00 25,00 25,00 5.00 5.00 2.00 2.00 5.00 5.00 2.00 2.00 2.00 2.00 1.00 1.00 1.50 1.50 1.50 1.50 - 3.00

EPDM rubber (BunaAP451 of Bunawerke Huels / FRG)

Buntwerke Huels EPDM rubber MBuna AP447 / FRG)

precipitated silica

chalk

kaolin

paraffinic process oil

Emulsion softener (Dolavon EW 960 of VEB Chemiewerk Greiz-Dölau / DDR) Polyethylene glycol

zinc oxide

stearic acid

N-cyclohexyl-2-benzothiazylsulfenamide

Tetramethylthiuramidisulfid

Zinc N-ethyl-N-phenyl-dithiocarbamate

sulfur

Inventive silane according to Preparation Example 4 285.00

288.00

Recipe D

Nitrile formulation, -Dölau / DDR) comparison invention Inventions heat-resistant mixture mixture , according to 001 002 mixture Butadiene nitrile rubber (28% acrylonitrile) 100.00 100.00 003 precipitated silica 40,00 40,00 chalk 20.00 20.00 Emulsion softener (Dolavon EW 960 of VEB Chemiewerk Greiz 4.00 4.00 zinc oxide 5.00 5.00 magnesia 10.00 10.00 stearic acid 1.50 1.50 Poly (2,2,4) trimethyl- (1,2) -dihydrochinolin 2.00 2.00 tetramethylthiuram 3.00 3.00 Bis (2-benzothiazyl) disulfide comparison 1.00 1.00 N, N'-dimorpholyl mixture 2.00 2.00 sulfur Year-soot 0.25 0.25 Silane according to the invention according to production process 4 001 - 3.50 total 178.75 192.25 Recipe E Natural rubber formulation comparison mixture 002

Natural Rubber, No. 1 RSS, masts 100,00

ISAF carbon black (P234) 60.00

precipitated silica

aromatic plasticizer *}! 3.00

Zinc oxide 5.00

Stearic acid 2.00

Ozone protection wax 2,00

N-phenyl-N'-isopropyl-p-phenylenediamine 1.50

N-phenyl-2-naphthylamine 1.50

N-cyclohexyl-2-benzothiazyl-sulfenamide 1.50

N- (cyclohexylthio) phthalimide 0.50

Sulfur 2.00

Inventive silane according to Preparation Example 4 -

Total 179.00

100.00 40.00 20.00 3.00 5.00 2.00 2.00 1.50 1.50 1.50 0.50 2.00

179.00

100.00 40.00 20.00 3.00 5.00 2.00 2.00 1.50 1.50 1.50 0.50 2.00 3.00

182.00

Recipe F SBR recipe

comparisons Inventive mixtures 003 004 mixture 100 100 001 00? 5 5 100 100 5 5 5 5 2 2 5 5 3 3 2 2 1.5 1.5 3 3 0.3 0.3 1.5 1.5 2.5 2.5 0.3 0.3 1 1 2.5 2.5 40 40 1 1 40 40

Styrene-butadiene rubber (Type SB 152 H) aromatic plasticizer oil zinc oxide stearic acid antiozonant wax N-cyclohexyl-2-be, nzot.hiazyl-sulfenamide T3tramethylthiunrnd;.; Sulfide sulfur 2-mercaptobenzimidazole precipitated silica according to the invention, according to manufacturer's instructions.

Example 6

16 total

160.3

163.3

163.3

All of the rubber compounds used were prepared according to the prior art two-stage mixing process on an internal laboratory mixer with subsequent homogenization on a laboratory roll mill. Between the preparation of the first and second mixing stage a storage time of at least 12 hours was observed. The examination of the dynamic and physical-mechanical characteristics of the individual mixtures of the respective recipe series according to the general TGL showed that the use of silanes of the invention, the processing security, the crosslinking behavior, the phys.-mech. Property profile and thus the reinforcing properties of Vulkanisate be improved to an unexpected extent. Thus, the S-containing silanes produced according to the invention can be regarded as excellent reinforcing additives or adhesion promoters for silically filled rubber mixtures.

Formulation A (SBR recipe) Mixing values

number (100 ° C) (RE) 001 002 003 004 005 006 Rheometer (15O ⁰ C) (Min: sec) Mooney ML (Min: sec) 69 49 56 57 61 65 ML1 / 4 t ₂ (Re) tgo 14.8 11.4 13.3 13.2 13 " 14.6 MH 9:22 9:51 8:09 7:23 6:33 6:34 32:05 17:42 18:08 15:42 17:24 18:41 70.0 69.7 74.6 74.6 74.6 76.0

Vulcanization at 140 ⁰ C (min) rod test standard rod 3

30

30

30

30

M 100 (MPa) 2.09 2.70 2.75 2.91 3.72 4.60 M 200 (M? A) 3.70 4.84 5.60 5.78 7.04 8.24 M 300 (MFa) 5.19 6.88 8.31 8.71 9.71 - O (%) 490 369 392 394 298 255 H (ShA) 52 54 54 56 56 56 bl.D. (%) 16 12 10 9 9 9 e (%) 36 44 38 39 40 46 RdV (%) 62.5 44.4 51.9 50.5 49.7 50.2

In the examples according to the invention significantly improved reinforcing properties are achieved with simultaneously improved elasticity, compression set and permanent elongation. The silane-added mixtures have favorable processing and crosslinking properties.

Recipe B (OeSBR / BR recipe) Mixing values

number (100 ⁰ C) 001 002 003 Mooney (12O ⁰ C) ML'Λ (Min.) 40 65 61 Mooney scorch (15O ⁰ C) t5 (RE) 31.1 32.4 34.1 rheometer (Min: sec) ML (RNIN: sec) 8.7 12.9 12.9 t2 (RE) 6:40 6:49 6:41 t90 18:47 27:12 22:36 MH 51.0 49.3 55.4

Cure at 15O ⁰ C

Ring test, standard ring 6mm

25min

35 min

30 min

M 100 (MPa) 1.60 1.49 2.37 M 200 (MPa) 4.40 3.15 5.52 M 300 (MPa) 8.57 5.03 8.66 F (MPa) 12.22 10.78 13.16 D (%) 424 572 476 H (ShA) 55 55 59 bl.D (%) 7 ? 0 15 e (%) 38 39 41 A (mm ³ ) 95 141 113 RdV (%) 30.7 48.6 31.7 (24h / 100 ° C) Roelig exam tan delta 0.201 0,189 0.166 e ' (MPa) 5.53 6.47 6.88 Steaming, rel. (%) 46.5 44.8 40.5

The vulcanizates of the mixture according to the invention have significantly increased reinforcing properties. In some cases they clearly exceed that of the soot mixture. The excellent dynamic properties significantly exceed the level of both examples. At the same time, the mixture according to the invention has increased processing safety and a favorable crosslinking behavior.

Recipe C (EPDM recipe) Mixing characteristics

Number Mooney Viscosity

Mooney scorch

rheometer

(100 ⁰ C) (120 ⁰ C) (min.) (15O ⁰ C) (RE) (min: sec) (min: sec) (RE)

001

002

66 60 9.5 8.9 10.3 11.2 1:48 1 -M 17:37 17:06 80.0 84.8 2.32 3.21 3.14 4.70 4.05 _ 4.24 5.12 330 248 72 74 20 10 38.5 35.8

Vulcanization (20 min / 160 "C)

Ring test, standard ring 6 mm

M100 (MPa)

M 200 (MPa)

M 300 (MPa)

F (MPa)

H (ShA)

bl. D (%)

RdV (%) (7d / 100 ° C)

In the example according to the invention significantly increased reinforcing properties are achieved with simultaneously improved compression set and permanent elongation. The mixture has favorable processing and crosslinking properties.

(Continuation) 001 002 003 number Mooney Flexometers exam Test duration 40 min 27.0 23.0 23.0 delta T (K) Roalig exam 0.154 0.171 0.143 tan delta 8.32 7.53 7.98 E '(MPa) 38.7 41.3 36.9 Steaming, rel. (%)

The vulcanizates of the mixture according to the invention have significantly higher reinforcing properties, they are comparable to those of the carbon black-filled mixture, while this is still significantly exceeded in terms of dynamic properties. The mixture according to the invention has favorable vulcanization and processing properties.

Formulation F (S8R recipe) Mixing characteristics

number (100 ⁰ C) 001 U '. 002 1.62 003 1.72 004 1.74 Mooney (15O ⁰ C) 1.74 2.66 2.88 3.09 ML 'Λ (RE) 58 2.38 59 3.48 55 3.84 61 4.06 rheometer (Min: sec) 4.35 4.33 4.48 4.51 Mu (Min: sec) 11.7 565 11.5 423 11.2 387 11.6 371 X ₁ (RE) 9:42 11 8:27 7 7:47 7 8:18 5 t " (Min) 16:49 55 15:22 59 13:18 60 14:07 61 MH 66.4 57 74.5 60 77.4 60 80.6 60 Vulcanization at 14O ⁰ C 30 30 30 30 bar exam (MPa) 52.0 47.8 44.0 41.7 Standard bar 3 (MPa) M 100 (MPa) 0.113 ₍ 0.093 0.082 0.083 M 200 (MPa) 6.68 6.87 7.45 8.10 M 300 (%) F (%) D (ShA) bl.D. (%) H e (%) (12.5 mm test specimen) RdV (24h / 100 ° C) - Roelig exam (MPa) tan delta e '

In the examples according to the invention, significantly improved reinforcing properties are achieved by the addition of silane with simultaneously improved elasticity, compression set and permanent elongation. In addition, an improvement of the dynamic behavior "(Rölig test) is ensured with favorable processing and crosslinking properties.

Recipe D (nitrile rubber formulation) Mixing characteristics

number (100 ⁰ C) 001 002 Mooney (12O ⁰ C) ML1 + 4 (Min.) 102 95 Mooney scorch (15O ⁰ C) t5 (RE) 9.3 11.8 rheometer (Minisec) ML (Min: sec) 18.4 17.0 t2 (RE) 2:50 2:55 t90 11:20 13:30 MH 95.5 111.7

Vulcanization (3? Nin / 150 ⁰ C) ring test, standard ring 6mm

M 100 (MPa) 2.72 3.47 M 200 (MPa) 5.43 - LL. (MPa) 7.25 7.22 D (%) 303 199 H (ShA) 73 74 bl.D (%) 7 3 RdV (%) 36.3 33.6 (7d / 125 ° C) aging (7d / 100 ° C) FZS (%) 12.8 -7.2 ZGD (%) 31.0 18.6 TE lnc'ex " (%) 60.1 87.3

• TE-Indox = 100 χ F χ D (aged) FxD (unaged)

In the example according to the invention substantially improved tension value, compression set and permanent elongation, as well as the aging behavior are improved, wherein the mixture has an increased processing safety and a high Vernetzungsorad.

Recipe E (natural rubber formulation) Mixing characteristics

number (100'C) (Min.) 001 002 003 Mooney Scorch (120 ⁰ C) (15O ⁰ C) Mooney t5 (RE) 56 65 64 ML1 + 4 rheometer (Min: sec) 31.4 35.7 33.1 ML (Min: sec) t2 t90 11.6 14.6 14.0 6:59 6:50 E: 19 10:58 11:21 10:02

MH (RE) 73.0 60.0 66.0

Vulcanization (15 min / 150 ⁰ C) Ring testing, standard ring 6mm

M 100 (MPa) M 200 (MPa) M 300 (MPa) F (MPa) D i%) H (ShA) bl.D (%) e (%) A (mm ³ ) RdV (%) (24 h / 100 ° C)

3.02 2.41 3.04 8.41 5.96 8.18 13.26 10.19 13,20 17.00 14.65 17.30 430 448 429 67 61 65 21 21 18 39 43 46 112 142 124 37.2 43.4 35.6

Claims (1)

1. A process for the preparation of sulfur-containing organosilicon compounds without the use of catalyst and at atmospheric pressure, characterized in that an organosilane or organosiloxane of the general formula R ¹ R ¹ Α-έΐ-R ^ or Α-άι
R * -o-si R ⁴ -R ³