DD299187B5 - Process for the preparation of sulfur-containing organosilicon compounds - Google Patents

Description

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 at temperatures above 420 K is reacted directly.

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, inter alia, for vehicle tire treads and carcasses. Furthermore, sulfur-containing silane coupling agents can be used in the manufacture of sealants, casting molds for metal casting, color and protective coatings, adhesives, asphalt mixtures and silicate-filled plastics. Finally, there are applications in the attachment of functional groups and drugs to inorganic supports, e.g. in the immobilization of enzymes, in the preparation of fixed-bed catalysts 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-organooxysilyUoligosulfide, 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 (DE 2542534, DE 2712966, DE 3311 340).

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 bisforganoorganooxysilydigigosulfides, preferably to give bis (propyl-organooxysilyl) oligosulfides. According to DE 2141160 S _z HaI ₂ (z = 1 to 3, Hai = Cl, Br) or according to DE 2405758 sulfur is used.

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

R ¹ R ¹

A-Si-R ² or Α-έϊ

R ³ R ⁵

-R ³

A = alkenyl, cycloalkenyl, cycloalkenylalkyl, alkenylaryl,

R ^{1 to} R ⁶ = each independently OR, A, alkyl, cycloalkyl, aryl,

R = A, alkyl, cycloalkyl, aryl and

π = 1 to 10 mean

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 A: sulfur or hydrogen sulfide = 1: 1 to 1: 5, at normal pressure and temperatures above 420K. The temperature range from 420 to 500K is preferred. When using a mixture of hydrogen sulfide and the mass fraction of sulfur is preferably between 10 ~ ² to

10 " ¹ 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. Because of their high sulfur content or a large number of potential linkage sites in the molecule, they are excellent silane coupling agents 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 which is dissolved in dry organic solvents such as ethanol

or N-N-dimethylformamide, is undecomposed soluble in any ratio.

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

explained.

Example 24

120 g (0.44 mol) of 4 (2-triethoxysilyl-ethylcyclohexene and 4 g (0.12 mol) of sulfur powder are placed in a 250 ml three-necked flask equipped with stirrer, internal thermometer, drying tube and gas inlet The reaction product is a yellow-green, in dry organic solvents, such as ethanol or Ν, Ν-dimethylformamide, undecomposed soluble in any ratio, clear, oily liquid obtained The 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

Examples of starting substances

No organo-organo sulfuric time

silane or siloxane [g] [mol] [g] [mol] [h]

1 4 (2-triethoxysilylethyl) 100 0.367

2 cyclohexene 3

11.8 0.367 0.5 23.5 0.734 1.0 35.3 1.1 1.5 47,07 1.468 3.0 58.84 1,835 5.0

6 Exo-8 and exo-9-triethoxysilyl 100 0.337 21.6 0.674 1.0 7 endotricyclo- 32.4 1,011 2.5 [5,2,1,0 ²⁶ ] dec-3-en 8th 5-Triethoxysilylbicyclo 43.3 1,348 4.0 9 [2,2,1] hept-2ene 80 0.312 20 0.624 2.0 10 30 0.936 3.5 11 40 1,248 5.0

Table 1 (continued)

12 5-diethoxymethylsilylbicyclo [2,2,1] hept-2-ene 80 0.353 34 1,060 3.5 13 14 15 (Trimethoxyethoxy) vinylsilane 80 0.285 18.3 27.4 36.5 0.57 0.855 1.14 4.0 6.0 8.0 16 17 1,3-divinyl-i, 1,3,3-tetraethoxydi- siloxane 80 0.261 16.7 25.1 0.522 0.783 2.0 4.0 18 19 20 Diethoxy (phenyl) vinylsilane 80 0.36 23.1 34.6 46.2 0.72 1.079 1.44 2.0 4.0 6.0 to to CO IO - ' Mixture of 4-triethoxysilyl-cyclopent-1-ene and 3-triethoxysilyl-cyclopent-i-ene 80 0,347 22.3 33.4 44.5 0.694 1.041 1.388 3.0 6.0 9.0

Table 1 (continued) Reaction products

yield

[% D.Th.

Analytical data [10 ² kg / kg]

C gef. ber. gef.

gef.

calc.

colour

1 97.9 54.89 55.22 9.10 9.27 10.23 10.5 yellow 2 98.0 48.31 48.96 8.21 8.38 19,01 19.05 yellow-orange 3 96.8 45.71 45.61 7.46 7.65 26.07 26,09 yellow-orange 4 95.2 41,15 41.96 7.40 7.04 30.73 32,00 orange CJL 95.1 32.32 32.85 5.25 5.52 36.82 37.04 red

6 7 8 98.3 97.4 97.7 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-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 5,70 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 25

Analogously to Example 24 with the following modifications:

- Template: 100 g (0.337 mol) of S-Triethoxysilyltricyclotö ^ J.O ^ ldec-S-en and 4g (0.12 mol) of sulfur powder

- Introduction of 1,21 (0,675 mol) hydrogen sulfide "

- reaction time: 1.5h "

Yield: 121 g (95.0% of theory)

- Elemental analysis:

Found .: C 53.24 H 8.27 S 17.41 calc .: C 53.00 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 which contain as fillers silicate fillers and optionally carbon black and sulfur and among other common accelerator systems. The term "siliceous fillers" is understood to mean rubbers that are compatible with rubber and can be incorporated into rubber mixtures which consist of silicates, contain silicates or contain chemically bonded silicates, especially light, natural, pyrogenic or precipitated silicas and synthetic silicates or naturally occurring silicates.

The silicate fillers mentioned are preferably used in amounts of 1 to 20OpHR (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 oil-extended styrenebutadiene rubber (type SBR 1712) 003 004 5 005 006 SBR recipe Recipe B mixture 1,4-cis-polybutadiene OeSBR / BR recipe 001 002 HAF carbon black (TypeP324) 100 100 3 100 100 precipitated silica 5 Styrene-butadiene 100 100 aromatic softener egg 10 10 10 10 Rubber (type SB 152 H) zinc oxide 5 5 5 5 aromatic 10 10 stearic acid 2 2 2 2 processing oil 5 5 N-phenyl-2-naphthylamine 1 1 1 1 zinc oxide 2 2 2 2 2 2 stearic acid 1 1 Ozone protection wax 5 2 1.5 1, 1.5 1.5 chalk N-cyclohexyl-2-benzo- 1.5 1.5 0.3 0 3 0.3 0.3 thiazyl-sulfenamide 2.5 2, 2.5 2.5 Tetramethylthiuramdi- 0.3 0.3 40 40 40 40 sulfide 2.5 2.5 N-phenyl-N'-isopropyl-p-phenylenediamine sulfur 40 40 Ozone protection wax precipitated silica - - - - Silane according to the invention N-cyclohexyl-2-benzothiazyl-sulfenamide 3 - - - according to manufacturing - 3 sulfur - 3 - - example 1 - - - - 3 - 2 - - - _ - 3 3 - - 167.3 167, 167.3 167.3 4 _ _ 5 167.3 167.3 comparison comparison Fiction mixture mixture gemaße Year-soot mixture 001 002 003 110.00 110.00 110.00 20.00 20.00 20.00 70,00 40,00 40,00 - 30.00 30.00 Inventive silane according to Preparation Example 4 7.50 7.50 7.50 3.00 3.00 3.00 1.00 1.00 1.00 1.50 1.50 1.50 1.50 1.50 1.50 2.00 2.00 2.00 1.50 1.50 1.50 2.50 2.50 2.50 - - 3.00

total

220.50

220.50

223.50

Recipe C

EPDM recipe

-5- 299 187 comparison 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)

EPDM rubber (Buna AP 447 of Bunawerke Huels / Germany)

precipitated silica

chalk

kaolin

paraffinic process oil

Emulsion softener (Dolavon EW960 of VEB ChemiewerkGreiz-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, comparison comparison invention Fiction heat-resistant mixture mixture mixture contemporary Year-soot 001 002 mixture Butadiene nitrile rubber (28% acrylonitrile) 001 100.00 100.00 003 precipitated silica 40,00 40,00 chalk 20.00 20.00 4.00 4.00 5.00 5.00 10.00 10.00 1.50 1.50 2.00 2.00 3.00 3.00 Emulsion softener (Dolavon EW 960 of VEB Chemiewerk Greiz-Dolau / DDR) 1.00 1.00 zinc oxide 2.00 2.00 magnesia 0.25 0.25 stearic acid - 3.50 Poly (2,2,4) trimethyl- (1,2) -dihydrochinolin 178.75 192.25 tetramethylthiuram Bis (2-benzothiazyl) disulfide comparison N, N'-dimorpholyl mixture sulfur Inventive silane according to Preparation Example 4 002 total Recipe E Natural rubber formulation

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

ISAF-RuB (P 234) 60,00

precipitated silica aromatic processing oil 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

comparatively Inventive mixtures 003 004 mixture 100 100 001 002 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-benzothiazyl-sulfenamide tetramethylthiuram disulfide sulfur 2-mercaptobenzimidazole precipitated silica Inventive silane according to Preparation Example 6

16 total

160.3

163.3

163.3

All the rubber mixtures used were prepared according to the prior art two-stage mixing method on a laboratory internal 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 characteristics

number (100 ⁰ C) (RE) 001 002 003 004 005 006 Rheometer (150 ° C) (Min: sec) Mooney viscosity ML (Min: sec) 69 49 56 57 61 65 MLV4 t ₂ (Re) tgo 14.8 11.4 13.3 13.2 13.8 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 14O 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 (MPa) 3.70 4.84 5.60 5.78 7.04 8.24 M 300 (MPa) 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 characteristics

number (100 ⁰ C) 001 002 003 Mooney (12O ⁰ C) MLV * (Min.) 40 65 61 Mooney scorch (150 ⁰ C) t5 (RE) 31.1 32.4 34.1 rheometer (Min: sec) ML (Minrsec) 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

Vulcanization at 150 ^° C. 25 min 35 min 30 min

Ring test, standard ring 6mm

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 20 15 e <%) 38 39 41 A (mm ³ ) 95 141 113 RdV (%) 30.7 48.6 31.7 (24 h / 100 ⁰ 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 considerably exceed the level of both comparative 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 001

Mooney

ML1 + 4 (100 ° C)

Mooney scorch (12O ⁰ C)

t5 (min.)

Rheometer (15O ⁰ C)

ML (RE)

t2 (min: sec)

t90 (min: sec)

MH (RE) 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.

66 60 9.5 8.9 10.3 11.2 1:48 1:47 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

Recipe D (nitrile rubber formulation) Mixing characteristics

number (100 ⁰ C) 001 002 Mooney viscosity (120 ⁰ C) ML1 +4 (Min.) 102 95 Mooney scorch (150x) t5 (RE) 9.3 11.8 rheometer (Min: sec) ML (Min: sec) 18.4 17.0 t2 (RE) 2:50 2:55 t90 11:20 13:30 MH 95.5 111.7

Vulcanization (30 min / 150 ⁰ C) Ring testing, standard ring 6mm

M 100 (MPa) 2.72 3.47 M 200 (MPa) 5.43 - F (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 Index * (%) 60.1 87.3

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

In the example according to the invention substantially improved stress 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 degree of crosslinking.

Recipe E (natural rubber formulation) Mixing characteristics

number (100 ° C) 001 002 003 Mooney viscosity (120 ° C) ML1 +4 (Min.) 56 65 64 Mooney scorch (150 ° C) 31.4 35.7 33.1 t5 (RE) rheometer (Min: sec) ML (min: see) 11.6 14.6 14.0 t2 (RE) 6:59 6:50 6:19 t90 10:58 11:21 10:02 MH 73.0 60.0 66.0

Vulcanization (15 min / 150 ⁰ C)

Ring test, standard ring 6mm

M100 (MPa)

M 200 (MPa)

M 300 (MPa)

F (MPa)

H (ShA)

bl.D (%)

A (mm ³ )

RdV (%) (24 h / 100 ⁰ 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

(Continuation) 001 002 003 number Mooney Flexometers exam Prufdauer40min 27.0 28.0 23.0 deltaT (K) Roelig 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 (SBR recipe) Mixing characteristics

number (100 ⁰ C) 001 1.21 002 1.62 003 1.72 004 1.74 Mooney (150 ° C) 1.74 2.66 2.88 3.09 ML ¹ A (RE) 58 2.38 59 3.48 55 3.84 61 4.06 rheometer (Min: sec) 4.35 4.33 4.48 4.51 M _L (Min: sec) 11.7 565 11.5 423 11.2 387 11.6 371 t ₂ (RE) 9:42 11 8:27 7 7:47 7 8:18 5 too (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 140 ^° 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 (24 h / 100 ⁰ C) - Rolig 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 in the dynamic behavior (Rolig test) is ensured with favorable processing and crosslinking properties.

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 A-Si-R ² or A-Si , 3 _R 5 -O-Si
R -R ³