Rubber compositions
Abstract
Kautschukmischungen, enthaltend Kautschuk, Füllstoffe, gegebenenfalls weitere Kautschukhilfsmittel und mindestens ein Organosilan der allgemeinen Formel I, R1R2R3SiR4-SH (I) wobei R1 Methyl oder Ethyl ist, R2 Methoxy, Ethoxy oder -O-(Y-O)m-X ist, mit Y= verzweigte oder unverzweigte, gesättigte oder ungesättigte zweibindige Kohlenwasserstoffgruppe, X eine C1- bis C9-Alkylgruppe und m=1-40 ist, R3 Methyl, Ethyl oder R2 ist, und R4 eine verzweigte oder unverzweigte, gesättigte oder ungesättigte, aliphatische, aromatische oder gemischt aliphatische /aromatische zweibindige C1-C12 Kohlenwasserstoffgruppe ist. Die erfindungsgemäßen Kautschukmischungen werden hergestellt durch mischen von Kautschuk, Füllstoff, gegebenenfalls weiteren Kautschukhilfsmitteln und mindestens einem Organosilan der allgemeinen Formel I. Die Kautschukmischungen können zur Herstellung von Formkörpern verwendet werden.
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14 claims: 8 independent, 6 dependent
- 1Kautschukmischungen, enthaltend Kautschuk, Füllstoffe, gegebenenfalls weitere Kautschukhilfsmittel und mindestens ein Organosilan der allgemeinen Formel I, R1R2R3SiR4-SH (I) wobei R1 Methyl oder Ethyl ist, R2 Methoxy, Ethoxy oder -O-(Y-O)m-X ist, mit Y= verzweigte oder unverzweigte, gesättigte oder ungesättigte zweibindige Kohlenwasserstoffgruppe, X eine C1- bis C9-Alkylgruppe und m=1-40 ist, R3 Methyl, Ethyl oder R2 ist und R4 eine verzweigte oder unverzweigte, gesättigte oder ungesättigte, aliphatische, aromatische oder gemischt aliphatische /aromatische zweibindige C1-C12 Kohlenwasserstoffgruppe ist. Rubber mixtures containing rubber, fillers, optionally further rubber auxiliaries and at least one organosilane of the general formula I, R1R2R3SiR4-SH (I) where R1 Is methyl or ethyl, R2 Methoxy, ethoxy or -O- (YO)m-X is, with Y = branched or unbranched, saturated or unsaturated divalent hydrocarbon group, X is a C1 to C9 alkyl group and m = 1-40, R3 Methyl, ethyl or R2 is and R4 a branched or unbranched, saturated or unsaturated, aliphatic, aromatic or mixed aliphatic / aromatic divalent C1-C12 Is hydrocarbon group.
- 2Kautschukmischungen gemäß Anspruch 1, dadurch gekennzeichnet, daß das Organosilan der allgemeinen Formel I oligomerisierte oder polymerisierte Organosilane der allgemeinen Formel I enthält. Rubber mixtures according to claim 1, characterized in that the organosilane of the general formula I contains oligomerized or polymerized organosilanes of the general formula I.
- 3Kautschukmischungen gemäß Anspruch 1, dadurch gekennzeichnet, daß das Organosilan der allgemeinen Formel I Dimethylethoxysilylpropylmercaptan, Methyldiethoxysilylpropylmercaptan, Diethylethoxysilylpropylmercaptan, Ethyldiethoxysilylpropylmercaptan, Dimethylmethoxysilylpropylmercaptan, Methyldimethoxysilylpropylmercaptan, Diethylmethoxysilylpropylmercaptan oder Ethyldimethoxysilylpropylmercaptan ist. Rubber mixtures according to claim 1, characterized in that the organosilane of the general formula I is dimethylethoxysilylpropyl mercaptan, methyldiethoxysilylpropylmercaptan, diethylethoxysilylpropylmercaptan, ethyldiethoxysilylpropylmercaptan, dimethylmethoxysilylpropylmercaptan, methyldimethoxysilylpropylmethoxysaptyl, ethylpylmercaptan
- 4Kautschukmischungen gemäß Anspruch 1, dadurch gekennzeichnet, daß das Kautschukhilfsmittel ein Polyalkylenglykol ist. Rubber mixtures according to claim 1, characterized in that the rubber auxiliary is a polyalkylene glycol.
- 5Process for the preparation of the rubber mixtures according to Claim 1, characterized in that the rubber, filler, optionally further rubber auxiliaries and at least one organosilane of the general formula I are mixed. Verfahren zur Herstellung der Kautschukmischungen gemäß Anspruch 1, dadurch gekennzeichnet, daß man den Kautschuk, Füllstoff, gegebenenfalls weitere Kautschukhilfsmittel und mindestens ein Organosilan der allgemeinen Formel I mischt.
- 6Use of the rubber mixture according to claim 1 for the production of moldings. Verwendung der Kautschukmischung gemäß Anspruch 1 zur Herstellung von Formkörpern.
- 7Use of the rubber mixture according to claim 6 for the production of pneumatic tires, tire treads, cable sheaths, hoses, drive belts, conveyor belts, roller coverings, tires, shoe soles, sealing rings and damping elements. Verwendung der Kautschukmischung gemäß Anspruch 6 zur Herstellung von Luftreifen, Reifenlaufflächen, Kabelmänteln, Schläuchen, Treibriemen, Förderbändern, Walzenbelägen, Reifen, Schuhsohlen, Dichtungsringen und Dämpfungselementen.
Independent claims7
174 paragraphs in 36 sections, as filed
The invention relates to rubber mixtures, a process for their production and their use.
It is known that hydrolyzable sulfur-containing organosilicon compounds are able to react with fillers containing hydroxyl groups, such as natural and synthetic silicates, carbonates, glasses and metal oxides. They are used for surface modification and adhesion mediation. In the rubber processing industry they are used as adhesion promoters between the reinforcing filler and the polymer used (Angew. Chem. 98, (1986) 237-253, DE2141159, DE2212239, DE19544469A1, US3978103, US4048206, EP784072A1). The best-known representatives of this class of substances include the polysulfans (alkyltrialkoxysilanes), such as, for example, bis [3-triethoxysilylpropyl] tetrasulfan or bis [3-triethoxysilylpropyl] disulfane.
Furthermore, the use of mercapto-functionalized organosilanes in rubber mixtures is known (US3350345, FR2.094.859). The use of alkylsilanes to lower the viscosity of rubber mixtures (EP795577A1, EP864605A2) and the combination of mercapto-functional silanes with longer-chain alkylsilanes (DE10015309A1) is also known.
A disadvantage of using the trialkoxy-functional silanes is the emission of volatile hydrocarbons, which in practice are mainly methanol and ethanol.
Dialkylmonoalkoxysilylpolysulfides are known from DE1043357A1 and EP1244676B1. Due to the dialkyl monoalkoxy group, the emission of volatile hydrocarbons is lower than with trialkoxy compounds.
The disadvantage of dialkyl monoalkoxysilyl polysulfides is the poor abrasion and tear resistance.
It is an object of the present invention to provide rubber mixtures which have a low emission of volatile hydrocarbons during their production and which have an improved tear resistance compared to rubber mixtures with known silanes.
The invention relates to rubber mixtures containing rubber, fillers, optionally further rubber auxiliaries and at least one organosilane of the general formula I, R<sup>1</sup>R<sup>2</sup>R<sup>3</sup>SiR<sup>4</sup>-SH (I) where R<sup>1</sup> Is methyl or ethyl, R<sup>2</sup> Methoxy, ethoxy or -O- (YO)<sub>m</sub>-X is, with Y = branched or unbranched, saturated or unsaturated divalent hydrocarbon group, preferably CH<sub>2</sub>, CH<sub>2</sub>CH<sub>2</sub>, CH<sub>2</sub>CH (CH<sub>3</sub>) or CH (CH<sub>3</sub>) CH<sub>2</sub>X is a C1 to C9 alkyl group, preferably methyl or ethyl, and m = 1-40, preferably 2-30, particularly preferably 3 to 25, very particularly preferably 4 to 20, extremely preferably 10 to 20, R<sup>3</sup> Methyl, ethyl or R<sup>2</sup> is and R<sup>4</sup> a branched or unbranched, saturated or unsaturated, aliphatic, aromatic or mixed aliphatic / aromatic divalent C<sub>1</sub>-C<sub>12</sub> Is hydrocarbon group.
At least one of the groups R<sup>2</sup> or R<sup>3</sup> an -O- (YO)<sub>m</sub>-X be a group.
The rubber mixtures can preferably be an organosilane of the general formula I R<sup>1</sup>R<sup>2</sup>R<sup>3</sup>SiR<sup>4</sup>-SH (I) where R<sup>1</sup> Is methyl or ethyl, R<sup>2</sup> equal to -O- (YO)<sub>m</sub>-X is, with Y = branched or unbranched, saturated or unsaturated divalent hydrocarbon group, preferably CH<sub>2</sub>, CH<sub>2</sub>CH<sub>2</sub>, CH<sub>2</sub>CH (CH<sub>3</sub>) or CH (CH<sub>3</sub>) CH<sub>2</sub>X is a C1 to C9 alkyl group, preferably methyl or ethyl, and m = 1-40, preferably 2-30, particularly preferably 3 to 25, very particularly preferably 4 to 20, extremely preferably 10 to 20, R<sup>3</sup> Methyl, ethyl, methoxy, ethoxy or R<sup>2</sup> is and R<sup>4</sup> a branched or unbranched, saturated or unsaturated, aliphatic, aromatic or mixed aliphatic / aromatic divalent C<sub>1</sub>-C<sub>12</sub> Hydrocarbon group is included.
R<sup>4</sup> can preferably CH<sub>2</sub>, CH<sub>2</sub>CH<sub>2</sub>, CH<sub>2</sub>CH<sub>2</sub>CH<sub>2</sub>, CH<sub>2</sub>CH<sub>2</sub>CH<sub>2</sub>CH<sub>2</sub>, CH (CH<sub>3</sub>), CH<sub>2</sub>CH (CH<sub>3</sub>), CH (CH<sub>3</sub>) CH<sub>2</sub>, C (CH<sub>3</sub>)<sub>2</sub>, CH (C<sub>2</sub>H<sub>5</sub>), CH<sub>2</sub>CH<sub>2</sub>CH (CH<sub>3</sub>) or CH<sub>2</sub>CH (CH<sub>3</sub>) CH<sub>2</sub> be.
As the organosilane of the general formula I, dimethylethoxysilylpropyl mercaptan, methyldiethoxysilylpropylmercaptan, diethylethoxysilylpropylmercaptan, ethyldiethoxysilylpropylmercaptan, dimethylmethoxysilylpropylmercaptan, methyldimethoxysilylpropylmercyloxypropyl, methyldimyl mercaptan,<sub>3</sub>O) (CH<sub>3</sub>) <sub>2</sub>Themselves<sub>2</sub>) <sub>2</sub>CH (CH<sub>3</sub>) -SH or (C<sub>2</sub>H<sub>5</sub>O) (CH<sub>3</sub>) <sub>2</sub>Themselves<sub>2</sub>) <sub>2</sub>CH (CH<sub>3</sub>) -SH can be used.
Compounds of formula I can be: [(C<sub>4</sub>H<sub>9</sub>O- (CH<sub>2</sub>-CH<sub>2</sub>O)<sub>2</sub>] (Me)<sub>2</sub>Themselves<sub>2</sub>)<sub>3</sub>SH, [(C<sub>4</sub>H<sub>9</sub>O- (CH<sub>2</sub>-CH<sub>2</sub>O)<sub>3</sub>] (Me)<sub>2</sub>Themselves<sub>2</sub>)<sub>3</sub>SH, [(C<sub>4</sub>H<sub>9</sub>O- (CH<sub>2</sub>-CH<sub>2</sub>O)<sub>4</sub>] (Me)<sub>2</sub>Themselves<sub>2</sub>)<sub>3</sub>SH, [(C<sub>4</sub>H<sub>9</sub>O- (CH<sub>2</sub>-CH<sub>2</sub>O)<sub>5</sub>] (Me)<sub>2</sub>Themselves<sub>2</sub>)<sub>3</sub>SH, [(C<sub>4</sub>H<sub>9</sub>O- (CH<sub>2</sub>-CH<sub>2</sub>O)<sub>6</sub>] (Me)<sub>2</sub>Themselves<sub>2</sub>)<sub>3</sub>SH, [(C<sub>5</sub>H<sub>11</sub>O- (CH<sub>2</sub>-CH<sub>2</sub>O)<sub>2</sub>] (Me)<sub>2</sub>Themselves<sub>2</sub>)<sub>3</sub>SH, [(C<sub>5</sub>H<sub>11</sub>O- (CH<sub>2</sub>-CH<sub>2</sub>O)<sub>3</sub>] (Me)<sub>2</sub>Themselves<sub>2</sub>)<sub>3</sub>SH, [(C<sub>5</sub>H<sub>11</sub>O- (CH<sub>2</sub>-CH<sub>2</sub>O)<sub>4</sub>] (Me)<sub>2</sub>Themselves<sub>2</sub>)<sub>3</sub>SH, [(C<sub>5</sub>H<sub>11</sub>O- (CH<sub>2</sub>-CH<sub>2</sub>O)<sub>5</sub>] (Me)<sub>2</sub>Themselves<sub>2</sub>)<sub>3</sub>SH, [(C<sub>5</sub>H<sub>11</sub>O- (CH<sub>2</sub>-CH<sub>2</sub>O)<sub>6</sub>] (Me)<sub>2</sub>Themselves<sub>2</sub>)<sub>3</sub>SH, [(C<sub>6</sub>H<sub>13</sub>O- (CH<sub>2</sub>-CH<sub>2</sub>O)<sub>2</sub>] (Me)<sub>2</sub>Themselves<sub>2</sub>)<sub>3</sub>SH, [(C<sub>6</sub>H<sub>13</sub>O- (CH<sub>2</sub>-CH<sub>2</sub>O)<sub>3</sub>] (Me)<sub>2</sub>Themselves<sub>2</sub>)<sub>3</sub>SH, [(C<sub>6</sub>H<sub>13</sub>O- (CH<sub>2</sub>-CH<sub>2</sub>O)<sub>4</sub>] (Me)<sub>2</sub>Themselves<sub>2</sub>)<sub>3</sub>SH, [(C<sub>6</sub>H<sub>13</sub>O- (CH<sub>2</sub>-CH<sub>2</sub>O)<sub>5</sub>] (Me)<sub>2</sub>Themselves<sub>2</sub>)<sub>3</sub>SH, [(C<sub>6</sub>H<sub>13</sub>O- (CH<sub>2</sub>-CH<sub>2</sub>O)<sub>6</sub>] (Me)<sub>2</sub>Themselves<sub>2</sub>)<sub>3</sub>SH, [(C<sub>7</sub>H<sub>15</sub>O- (CH<sub>2</sub>-CH<sub>2</sub>O)<sub>2</sub>] (Me)<sub>2</sub>Themselves<sub>2</sub>)<sub>3</sub>SH, [(C<sub>7</sub>H<sub>15</sub>O- (CH<sub>2</sub>-CH<sub>2</sub>O)<sub>3</sub>] (Me)<sub>2</sub>Themselves<sub>2</sub>)<sub>3</sub>SH, [(C<sub>7</sub>H<sub>15</sub>O- (CH<sub>2</sub>-CH<sub>2</sub>O)<sub>4</sub>] (Me)<sub>2</sub>Themselves<sub>2</sub>)<sub>3</sub>SH, [(C<sub>7</sub>H<sub>15</sub>O- (CH<sub>2</sub>-CH<sub>2</sub>O)<sub>5</sub>] (Me)<sub>2</sub>Themselves<sub>2</sub>)<sub>3</sub>SH, [(C<sub>7</sub>H<sub>15</sub>O- (CH<sub>2</sub>-CH<sub>2</sub>O)<sub>6</sub>] (Me)<sub>2</sub>Themselves<sub>2</sub>)<sub>3</sub>SH, [(C<sub>8</sub>H<sub>17</sub>O- (CH<sub>2</sub>-CH<sub>2</sub>O)<sub>2</sub>] (Me) <sub>2</sub>Themselves<sub>2</sub>) <sub>3</sub>SH, [(C<sub>8</sub>H<sub>17</sub>O- (CH<sub>2</sub>-CH<sub>2</sub>O)<sub>3</sub>] (Me) <sub>2</sub>Themselves<sub>2</sub>) <sub>3</sub>SH, [(C<sub>8</sub>H<sub>17</sub>O- (CH<sub>2</sub>-CH<sub>2</sub>O)<sub>4</sub>] (Me) <sub>2</sub>Themselves<sub>2</sub>) <sub>3</sub>SH, [(C<sub>8</sub>H<sub>17</sub>O- (CH<sub>2</sub>-CH<sub>2</sub>O)<sub>5</sub>] (Me) <sub>2</sub>Themselves<sub>2</sub>) <sub>3</sub>SH, [(C<sub>8</sub>H<sub>17</sub>O- (CH<sub>2</sub>-CH<sub>2</sub>O)<sub>6</sub>] (Me) <sub>2</sub>Themselves<sub>2</sub>) <sub>3</sub>SH, [(C<sub>9</sub>H<sub>19</sub>O- (CH<sub>2</sub>-CH<sub>2</sub>O)<sub>2</sub>] (Me)<sub>2</sub>Themselves<sub>2</sub>)<sub>3</sub>SH, [(C<sub>9</sub>H<sub>19</sub>O- (CH<sub>2</sub>-CH<sub>2</sub>O)<sub>3</sub>] (Me)<sub>2</sub>Themselves<sub>2</sub>)<sub>3</sub>SH, [(C<sub>9</sub>H<sub>19</sub>O- (CH<sub>2</sub>-CH<sub>2</sub>O)<sub>4</sub>] (Me)<sub>2</sub>Themselves<sub>2</sub>)<sub>3</sub>SH, [(C<sub>9</sub>H<sub>19</sub>O- (CH<sub>2</sub>-CH<sub>2</sub>O)<sub>5</sub>] (Me)<sub>2</sub>Themselves<sub>2</sub>)<sub>3</sub>SH, [(C<sub>9</sub>H<sub>19</sub>O- (CH<sub>2</sub>-CH<sub>2</sub>O)<sub>6</sub>] (Me)<sub>2</sub>Themselves<sub>2</sub>)<sub>3</sub>SH, [(C<sub>4</sub>H<sub>9</sub>O- (CH<sub>2</sub>-CH<sub>2</sub>O)<sub>2</sub>]<sub>2</sub>(Me) Si (CH<sub>2</sub>)<sub>3</sub>SH, [(C<sub>4</sub>H<sub>9</sub>O- (CH<sub>2</sub>-CH<sub>2</sub>O)<sub>3</sub>]<sub>2</sub>(Me) Si (CH<sub>2</sub>)<sub>3</sub>SH, [(C<sub>4</sub>H<sub>9</sub>O- (CH<sub>2</sub>-CH<sub>2</sub>O)<sub>4</sub>]<sub>2</sub>(Me) Si (CH<sub>2</sub>)<sub>3</sub>SH, [(C<sub>4</sub>H<sub>9</sub>O- (CH<sub>2</sub>-CH<sub>2</sub>O)<sub>5</sub>]<sub>2</sub>(Me) Si (CH<sub>2</sub>)<sub>3</sub>SH, [(C<sub>4</sub>H<sub>9</sub>O- (CH<sub>2</sub>-CH<sub>2</sub>O)<sub>6</sub>]<sub>2</sub>(Me) Si (CH<sub>2</sub>)<sub>3</sub>SH, [(C<sub>5</sub>H<sub>11</sub>O- (CH<sub>2</sub>-CH<sub>2</sub>O)<sub>2</sub>]<sub>2</sub>(Me) Si (CH<sub>2</sub>)<sub>3</sub>SH, [(C<sub>5</sub>H<sub>11</sub>O- (CH<sub>2</sub>-CH<sub>2</sub>O)<sub>3</sub>]<sub>2</sub>(Me) Si (CH<sub>2</sub>)<sub>3</sub>SH, [(C<sub>5</sub>H<sub>11</sub>O- (CH<sub>2</sub>-CH<sub>2</sub>O)<sub>4</sub>]<sub>2</sub>(Me) Si (CH<sub>2</sub>)<sub>3</sub>SH, [(C<sub>5</sub>H<sub>11</sub>O- (CH<sub>2</sub>-CH<sub>2</sub>O)<sub>5</sub>]<sub>2</sub>(Me) Si (CH<sub>2</sub>)<sub>3</sub>SH, [(C<sub>5</sub>H<sub>11</sub>O- (CH<sub>2</sub>-CH<sub>2</sub>O)<sub>6</sub>]<sub>2</sub>(Me) Si (CH<sub>2</sub>)<sub>3</sub>SH, [(C<sub>6</sub>H<sub>13</sub>O- (CH<sub>2</sub>-CH<sub>2</sub>O)<sub>2</sub>]<sub>2</sub>(Me) Si (CH<sub>2</sub>)<sub>3</sub>SH, [(C<sub>6</sub>H<sub>13</sub>O- (CH<sub>2</sub>-CH<sub>2</sub>O)<sub>3</sub>]<sub>2</sub>(Me) Si (CH<sub>2</sub>)<sub>3</sub>SH, [(C<sub>6</sub>H<sub>13</sub>O- (CH<sub>2</sub>-CH<sub>2</sub>O)<sub>4</sub>]<sub>2</sub>(Me) Si (CH<sub>2</sub>)<sub>3</sub>SH, [(C<sub>6</sub>H<sub>13</sub>O- (CH<sub>2</sub>-CH<sub>2</sub>O)<sub>5</sub>]<sub>2</sub>(Me) Si (CH<sub>2</sub>)<sub>3</sub>SH, [(C<sub>6</sub>H<sub>13</sub>O- (CH<sub>2</sub>-CH<sub>2</sub>O)<sub>6</sub>]<sub>2</sub>(Me) Si (CH<sub>2</sub>)<sub>3</sub>SH, [(C<sub>7</sub>H<sub>15</sub>O- (CH<sub>2</sub>-CH<sub>2</sub>O)<sub>2</sub>]<sub>2</sub>(Me) Si (CH<sub>2</sub>)<sub>3</sub>SH, [(C<sub>7</sub>H<sub>15</sub>O- (CH<sub>2</sub>-CH<sub>2</sub>O)<sub>3</sub>]<sub>2</sub>(Me) Si (CH<sub>2</sub>)<sub>3</sub>SH, [(C<sub>7</sub>H<sub>15</sub>O- (CH<sub>2</sub>-CH<sub>2</sub>O)<sub>4</sub>]<sub>2</sub>(Me) Si (CH<sub>2</sub>)<sub>3</sub>SH, [(C<sub>7</sub>H<sub>15</sub>O- (CH<sub>2</sub>-CH<sub>2</sub>O)<sub>5</sub>]<sub>2</sub>(Me) Si (CH<sub>2</sub>)<sub>3</sub>SH, [(C<sub>7</sub>H<sub>15</sub>O- (CH<sub>2</sub>-CH<sub>2</sub>O)<sub>6</sub>]<sub>2</sub>(Me) Si (CH<sub>2</sub>)<sub>3</sub>SH, [(C<sub>8</sub>H<sub>17</sub>O- (CH<sub>2</sub>-CH<sub>2</sub>O)<sub>2</sub>]<sub>2</sub>(Me) Si (CH<sub>2</sub>)<sub>3</sub>SH, [(C<sub>8</sub>H<sub>17</sub>O- (CH<sub>2</sub>-CH<sub>2</sub>O)<sub>3</sub>]<sub>2</sub>(Me) Si (CH<sub>2</sub>)<sub>3</sub>SH, [(C<sub>8</sub>H<sub>17</sub>O- (CH<sub>2</sub>-CH<sub>2</sub>O)<sub>4</sub>]<sub>2</sub>(Me) Si (CH<sub>2</sub>)<sub>3</sub>SH, [(C<sub>8</sub>H<sub>17</sub>O- (CH<sub>2</sub>-CH<sub>2</sub>O)<sub>5</sub>]<sub>2</sub>(Me) Si (CH<sub>2</sub>)<sub>3</sub>SH, [(C<sub>8</sub>H<sub>17</sub>O- (CH<sub>2</sub>-CH<sub>2</sub>O)<sub>6</sub>]<sub>2</sub>(Me) Si (CH<sub>2</sub>)<sub>3</sub>SH, [(C<sub>9</sub>H<sub>19</sub>O- (CH<sub>2</sub>-CH<sub>2</sub>O)<sub>2</sub>]<sub>2</sub>(Me) Si (CH<sub>2</sub>)<sub>3</sub>SH, [(C<sub>9</sub>H<sub>19</sub>O- (CH<sub>2</sub>-CH<sub>2</sub>O)<sub>3</sub>]<sub>2</sub>(Me) Si (CH<sub>2</sub>)<sub>3</sub>SH, [(C<sub>9</sub>H<sub>19</sub>O- (CH<sub>2</sub>-CH<sub>2</sub>O)<sub>4</sub>]<sub>2</sub>(Me) Si (CH<sub>2</sub>)<sub>3</sub>SH, [(C<sub>9</sub>H<sub>19</sub>O- (CH<sub>2</sub>-CH<sub>2</sub>O)<sub>5</sub>]<sub>2</sub> (Me) Si (CH<sub>2</sub>)<sub>3</sub>SH, [(C<sub>9</sub>H<sub>19</sub>O- (CH<sub>2</sub>-CH<sub>2</sub>O)<sub>6</sub>]<sub>2</sub>(Me) Si (CH<sub>2</sub>)<sub>3</sub>SH, [(C<sub>4</sub>H<sub>9</sub>O- (CH<sub>2</sub>-CH<sub>2</sub>O)<sub>2</sub>] (Me) (EtO) Si (CH<sub>2</sub>)<sub>3</sub>SH, [(C<sub>4</sub>H<sub>9</sub>O- (CH<sub>2</sub>-CH<sub>2</sub>O)<sub>3</sub>] (Me) (EtO) Si (CH<sub>2</sub>)<sub>3</sub>SH, [(C<sub>4</sub>H<sub>9</sub>O- (CH<sub>2</sub>-CH<sub>2</sub>O)<sub>4</sub>] (Me) (EtO) Si (CH<sub>2</sub>)<sub>3</sub>SH, [(C<sub>4</sub>H<sub>9</sub>O- (CH<sub>2</sub>-CH<sub>2</sub>O)<sub>5</sub>] (Me) (EtO) Si (CH<sub>2</sub>)<sub>3</sub>SH, [(C<sub>4</sub>H<sub>9</sub>O- (CH<sub>2</sub>-CH<sub>2</sub>O)<sub>6</sub>] (Me) (EtO) Si (CH<sub>2</sub>)<sub>3</sub>SH, [(C<sub>5</sub>H<sub>11</sub>O- (CH<sub>2</sub>-CH<sub>2</sub>O)<sub>2</sub>] (Me) (EtO) Si (CH<sub>2</sub>)<sub>3</sub>SH, [(C<sub>5</sub>H<sub>11</sub>O- (CH<sub>2</sub>-CH<sub>2</sub>O)<sub>3</sub>] (Me) (EtO) Si (CH<sub>2</sub>) <sub>3</sub>SH, [(C<sub>5</sub>H<sub>11</sub>O- (CH<sub>2</sub>-CH<sub>2</sub>O)<sub>4</sub>] (Me) (EtO) Si (CH<sub>2</sub>) <sub>3</sub>SH, [(C<sub>5</sub>H<sub>11</sub>O- (CH<sub>2</sub>-CH<sub>2</sub>O)<sub>5</sub>] (Me) (EtO) Si (CH<sub>2</sub>) <sub>3</sub>SH, [(C<sub>5</sub>H<sub>11</sub>O- (CH<sub>2</sub>-CH<sub>2</sub>O)<sub>6</sub>] (Me) (EtO) Si (CH<sub>2</sub>) <sub>3</sub>SH, [(C<sub>6</sub>H<sub>13</sub>O- (CH<sub>2</sub>-CH<sub>2</sub>O)<sub>2</sub>] (Me) (EtO) Si (CH<sub>2</sub>) <sub>3</sub>SH, [(C<sub>6</sub>H<sub>13</sub>O- (CH<sub>2</sub>-CH<sub>2</sub>O)<sub>3</sub>] (Me) (EtO) Si (CH<sub>2</sub>) <sub>3</sub>SH, [(C<sub>6</sub>H<sub>13</sub>O- (CH<sub>2</sub>-CH<sub>2</sub>O)<sub>4</sub>] (Me) (EtO) Si (CH<sub>2</sub>)<sub>3</sub>SH, [(C<sub>6</sub>H<sub>13</sub>O- (CH<sub>2</sub>-CH<sub>2</sub>O)<sub>5</sub>] (Me) (EtO) Si (CH<sub>2</sub>) <sub>3</sub>SH, [(C<sub>6</sub>H<sub>13</sub>O- (CH<sub>2</sub>-CH<sub>2</sub>O)<sub>6</sub>] (Me) (EtO) Si (CH<sub>2</sub>) <sub>3</sub>SH, [(C<sub>7</sub>H<sub>15</sub>O- (CH<sub>2</sub>-CH<sub>2</sub>O)<sub>2</sub>] (Me) (EtO) Si (CH<sub>2</sub>) <sub>3</sub>SH, [(C<sub>7</sub>H<sub>15</sub>O- (CH<sub>2</sub>-CH<sub>2</sub>O)<sub>3</sub>] (Me) (EtO) Si (CH<sub>2</sub>)<sub>3</sub>SH, [(C<sub>7</sub>H<sub>15</sub>O- (CH<sub>2</sub>-CH<sub>2</sub>O)<sub>4</sub>] (Me) (EtO) Si (CH<sub>2</sub>)<sub>3</sub>SH, [(C<sub>7</sub>H<sub>15</sub>O- (CH<sub>2</sub>-CH<sub>2</sub>O)<sub>5</sub>] (Me) (EtO) Si (CH<sub>2</sub>)<sub>3</sub>SH, [(C<sub>7</sub>H<sub>15</sub>O- (CH<sub>2</sub>-CH<sub>2</sub>O)<sub>6</sub>] (Me) (EtO) Si (CH<sub>2</sub>)<sub>3</sub>SH, [(C<sub>8</sub>H<sub>17</sub>O- (CH<sub>2</sub>-CH<sub>2</sub>O)<sub>2</sub>] (Me) (EtO) Si (CH<sub>2</sub>)<sub>3</sub>SH, [(C<sub>8</sub>H<sub>17</sub>O- (CH<sub>2</sub>-CH<sub>2</sub>O)<sub>3</sub>] (Me) (EtO) Si (CH<sub>2</sub>)<sub>3</sub>SH, [(C<sub>8</sub>H<sub>17</sub>O- (CH<sub>2</sub>-CH<sub>2</sub>O)<sub>4</sub>] (Me) (EtO) Si (CH<sub>2</sub>)<sub>3</sub>SH, [(C<sub>8</sub>H<sub>17</sub>O- (CH<sub>2</sub>-CH<sub>2</sub>O)<sub>5</sub>] (Me) (EtO) Si (CH<sub>2</sub>)<sub>3</sub>SH, [(C<sub>8</sub>H<sub>17</sub>O- (CH<sub>2</sub>-CH<sub>2</sub>O)<sub>6</sub>] (Me) (EtO) Si (CH<sub>2</sub>)<sub>3</sub>SH, [(C<sub>9</sub>H<sub>19</sub>O- (CH<sub>2</sub>-CH<sub>2</sub>O)<sub>2</sub>] (Me) (EtO) Si (CH<sub>2</sub>)<sub>3</sub>SH, [(C<sub>9</sub>H<sub>19</sub>O- (CH<sub>2</sub>-CH<sub>2</sub>O)<sub>3</sub>] (Me) (EtO) Si (CH<sub>2</sub>)<sub>3</sub>SH, [(C<sub>9</sub>H<sub>19</sub>O- (CH<sub>2</sub>-CH<sub>2</sub>O)<sub>4</sub>] (Me) (EtO) Si (CH<sub>2</sub>) <sub>3</sub>SH, [(C<sub>9</sub>H<sub>19</sub>O- (CH<sub>2</sub>-CH<sub>2</sub>O) <sub>5</sub>] (Me) (EtO) Si (CH<sub>2</sub>) <sub>3</sub>SH, [(C<sub>9</sub>H<sub>19</sub>O- (CH<sub>2</sub>-CH<sub>2</sub>O) <sub>6</sub>] (Me) (EtO) Si (CH<sub>2</sub>) <sub>3</sub>SH, [(C<sub>4</sub>H<sub>9</sub>O- (CH<sub>2</sub>-CH<sub>2</sub>O) <sub>2</sub>] (Me) (MeO) Si (CH<sub>2</sub>) <sub>3</sub>SH, [(C<sub>4</sub>H<sub>9</sub>O- (CH<sub>2</sub>-CH<sub>2</sub>O) <sub>3</sub>] (Me) (MeO) Si (CH<sub>2</sub>) <sub>3</sub>SH, [(C<sub>4</sub>H<sub>9</sub>O- (CH<sub>2</sub>-CH<sub>2</sub>O) <sub>4</sub>] (Me) (MeO) Si (CH<sub>2</sub>) <sub>3</sub>SH, [(C<sub>4</sub>H<sub>9</sub>O- (CH<sub>2</sub>-CH<sub>2</sub>O) <sub>5</sub>] (Me) (MeO) Si (CH<sub>2</sub>) <sub>3</sub>SH, [(C<sub>4</sub>H<sub>9</sub>O- (CH<sub>2</sub>-CH<sub>2</sub>O) <sub>6</sub>] (Me) (MeO) Si (CH<sub>2</sub>) <sub>3</sub>SH, [(C<sub>5</sub>H<sub>11</sub>O- (CH<sub>2</sub>-CH<sub>2</sub>O) <sub>2</sub>] (Me) (MeO) Si (CH<sub>2</sub>) <sub>3</sub>SH, [(C<sub>5</sub>H<sub>11</sub>O- (CH<sub>2</sub>-CH<sub>2</sub>O) <sub>3</sub>] (Me) (MeO) Si (CH<sub>2</sub>) <sub>3</sub>SH, [(C<sub>5</sub>H<sub>11</sub>O- (CH<sub>2</sub>-CH<sub>2</sub>O)<sub>4</sub>] (Me) (MeO) Si (CH<sub>2</sub>)<sub>3</sub>SH, [(C<sub>5</sub>H<sub>11</sub>O- (CH<sub>2</sub>-CH<sub>2</sub>O)<sub>5</sub>] (Me) (MeO) Si (CH<sub>2</sub>)<sub>3</sub>SH, [(C<sub>5</sub>H<sub>11</sub>O- (CH<sub>2</sub>-CH<sub>2</sub>O)<sub>6</sub>] (Me) (MeO) Si (CH<sub>2</sub>)<sub>3</sub>SH, [(C<sub>6</sub>H<sub>13</sub>O- (CH<sub>2</sub>-CH<sub>2</sub>O)<sub>2</sub>] (Me) (MeO) Si (CH<sub>2</sub>)<sub>3</sub>SH, [(C<sub>6</sub>H<sub>13</sub>O- (CH<sub>2</sub>-CH<sub>2</sub>O)<sub>3</sub>] (Me) (MeO) Si (CH<sub>2</sub>)<sub>3</sub>SH, [(C<sub>6</sub>H<sub>13</sub>O- (CH<sub>2</sub>-CH<sub>2</sub>O)<sub>4</sub>] (Me) (MeO) Si (CH<sub>2</sub>)<sub>3</sub>SH, [(C<sub>6</sub>H<sub>13</sub>O- (CH<sub>2</sub>-CH<sub>2</sub>O)<sub>5</sub>] (Me) (MeO) Si (CH<sub>2</sub>)<sub>3</sub>SH, [(C<sub>6</sub>H<sub>13</sub>O- (CH<sub>2</sub>-CH<sub>2</sub>O)<sub>6</sub>] (Me) (MeO) Si (CH<sub>2</sub>)<sub>3</sub>SH, [(C<sub>7</sub>H<sub>15</sub>O- (CH<sub>2</sub>-CH<sub>2</sub>O)<sub>2</sub>] (Me) (MeO) Si (CH<sub>2</sub>)<sub>3</sub>SH, [(C<sub>7</sub>H<sub>15</sub>O- (CH<sub>2</sub>-CH<sub>2</sub>O)<sub>3</sub>] (Me) (MeO) Si (CH<sub>2</sub>)<sub>3</sub>SH, [(C<sub>7</sub>H<sub>15</sub>O- (CH<sub>2</sub>-CH<sub>2</sub>O)<sub>4</sub>] (Me) (MeO) Si (CH<sub>2</sub>) <sub>3</sub>SH, [(C<sub>7</sub>H<sub>15</sub>O- (CH<sub>2</sub>-CH<sub>2</sub>O)<sub>5</sub>] (Me) (MeO) Si (CH<sub>2</sub>) <sub>3</sub>SH, [(C<sub>7</sub>H<sub>15</sub>O- (CH<sub>2</sub>-CH<sub>2</sub>O)<sub>6</sub>] (Me) (MeO) Si (CH<sub>2</sub>) <sub>3</sub>SH, [(C<sub>8</sub>H<sub>17</sub>O- (CH<sub>2</sub>-CH<sub>2</sub>O)<sub>2</sub>] (Me) (MeO) Si (CH<sub>2</sub>) <sub>3</sub>SH, [(C<sub>8</sub>H<sub>17</sub>O- (CH<sub>2</sub>-CH<sub>2</sub>O)<sub>3</sub>] (Me) (MeO) Si (CH<sub>2</sub>) <sub>3</sub>SH, [(C<sub>8</sub>H<sub>17</sub>O- (CH<sub>2</sub>-CH<sub>2</sub>O)<sub>4</sub>] (Me) (MeO) Si (CH<sub>2</sub>) <sub>3</sub>SH, [(C<sub>8</sub>H<sub>17</sub>O- (CH<sub>2</sub>-CH<sub>2</sub>O)<sub>5</sub>] (Me) (MeO) Si (CH<sub>2</sub>) <sub>3</sub>SH, [(C<sub>8</sub>H<sub>17</sub>O- (CH<sub>2</sub>-CH<sub>2</sub>O)<sub>6</sub>] (Me) (MeO) Si (CH<sub>2</sub>) <sub>3</sub>SH, [(C<sub>9</sub>H<sub>19</sub>O- (CH<sub>2</sub>-CH<sub>2</sub>O)<sub>2</sub>] (Me) (MeO) Si (CH<sub>2</sub>) <sub>3</sub>SH, [(C<sub>9</sub>H<sub>19</sub>O- (CH<sub>2</sub>-CH<sub>2</sub>O)<sub>3</sub>] (Me) (MeO) Si (CH<sub>2</sub>) <sub>3</sub>SH, [(C<sub>9</sub>H<sub>19</sub>O- (CH<sub>2</sub>-CH<sub>2</sub>O)<sub>4</sub>] (Me) (MeO) Si (CH<sub>2</sub>)<sub>3</sub>SH, [(C<sub>9</sub>H<sub>19</sub>O- (CH<sub>2</sub>-CH<sub>2</sub>O)<sub>5</sub>] (Me) (MeO) Si (CH<sub>2</sub>)<sub>3</sub>SH or (C.<sub>9</sub>H<sub>19</sub>O- (CH<sub>2</sub>-CH<sub>2</sub>O)<sub>6</sub>] (Me) (MeO) Si (CH<sub>2</sub>)<sub>3</sub>SH, with Me = CH<sub>3</sub> and Et = CH<sub>2</sub>CH<sub>3</sub>.
Compounds of formula I with X = C<sub>3</sub>H<sub>7</sub>, C<sub>4</sub>H<sub>9</sub>, C<sub>5</sub>H<sub>11</sub>, C<sub>6</sub>H<sub>13</sub>, C<sub>7</sub>H<sub>15</sub>, C<sub>8</sub>H<sub>17</sub> or C<sub>9</sub>H<sub>19</sub> can be: [(XO- (CH<sub>2</sub>-CH (CH<sub>3</sub>)O-)<sub>2</sub>] (Me) (MeO) Si (CH<sub>2</sub>)<sub>3</sub>SH, [(XO- (CH<sub>2</sub>-CH (CH<sub>3</sub>)O-)<sub>3</sub>] (Me) (MeO) Si (CH<sub>2</sub>)<sub>3</sub>SH, [(XO- (CH<sub>2</sub>-CH (CH<sub>3</sub>)O-)<sub>4</sub>] (Me) (MeO) Si (CH<sub>2</sub>)<sub>3</sub>SH, [(XO- (CH<sub>2</sub>-CH (CH<sub>3</sub>)O-)<sub>5</sub>] (Me) (MeO) Si (CH<sub>2</sub>)<sub>3</sub>SH, [(XO- (CH<sub>2</sub>-CH (CH<sub>3</sub>)O-)<sub>6</sub>] (Me) (MeO) Si (CH<sub>2</sub>)<sub>3</sub>SH, [(XO- (CH<sub>2</sub>-CH (CH<sub>3</sub>)O-)<sub>7</sub>] (Me) (MeO) Si (CH<sub>2</sub>)<sub>3</sub>SH, [(XO- (CH<sub>2</sub>-CH (CH<sub>3</sub>)O-)<sub>8</sub>] (Me) (MeO) Si (CH<sub>2</sub>)<sub>3</sub>SH, [(XO- (CH<sub>2</sub>-CH (CH<sub>3</sub>)O-)<sub>9</sub>] (Me) (MeO) Si (CH<sub>2</sub>)<sub>3</sub>SH, [(XO- (CH<sub>2</sub>-CH (CH<sub>3</sub>)O-)<sub>10</sub>] (Me) (MeO) Si (CH<sub>2</sub>)<sub>3</sub>SH, [(XO- (CH<sub>2</sub>-CH (CH<sub>3</sub>)O-)<sub>11</sub>] (Me) (MeO) Si (CH<sub>2</sub>)<sub>3</sub>SH, [(XO- (CH<sub>2</sub>-CH (CH<sub>3</sub>)O-)<sub>12</sub>] (Me) (MeO) Si (CH<sub>2</sub>)<sub>3</sub>SH, [(XO- (CH<sub>2</sub>-CH (CH<sub>3</sub>)O-)<sub>13</sub>] (Me) (MeO) Si (CH<sub>2</sub>)<sub>3</sub>SH, [(XO- (CH<sub>2</sub>-CH (CH<sub>3</sub>)O-)<sub>14</sub>] (Me) (MeO) Si (CH<sub>2</sub>)<sub>3</sub>SH, [(XO- (CH<sub>2</sub>-CH (CH<sub>3</sub>)O-)<sub>15</sub>] (Me) (MeO) Si (CH<sub>2</sub>)<sub>3</sub>SH, [(XO- (CH<sub>2</sub>-CH (CH<sub>3</sub>)O-)<sub>16</sub>] (Me) (MeO) Si (CH<sub>2</sub>)<sub>3</sub>SH, [(XO- (CH<sub>2</sub>-CH (CH<sub>3</sub>) O-)<sub>17</sub>] (Me) (MeO) Si (CH<sub>2</sub>) <sub>3</sub>SH, [(XO- (CH<sub>2</sub>-CH (CH<sub>3</sub>) O-)<sub>18</sub>] (Me) (MeO) Si (CH<sub>2</sub>) <sub>3</sub>SH, [(XO- (CH<sub>2</sub>-CH (CH<sub>3</sub>) O-)<sub>19</sub>] (Me) (MeO) Si (CH<sub>2</sub>) <sub>3</sub>SH, [(XO- (CH<sub>2</sub>-CH (CH<sub>3</sub>) O-)<sub>20</sub>] (Me) (MeO) Si (CH<sub>2</sub>) <sub>3</sub>SH, [(XO- (CH<sub>2</sub>-CH (CH<sub>3</sub>) O-)<sub>2</sub>] (Me) (EtO) Si (CH<sub>2</sub>) <sub>3</sub>SH, [(XO- (CH<sub>2</sub>-CH (CH<sub>3</sub>)O-)<sub>3</sub>] (Me) (EtO) Si (CH<sub>2</sub>) <sub>3</sub>SH, [(XO- (CH<sub>2</sub>-CH (CH<sub>3</sub>)O-)<sub>4</sub>] (Me) (EtO) Si (CH<sub>2</sub>) <sub>3</sub>SH, [(XO- (CH<sub>2</sub>-CH (CH<sub>3</sub>)O-)<sub>5</sub>] (Me) (EtO) Si (CH<sub>2</sub>) <sub>3</sub>SH, [(XO- (CH<sub>2</sub>-CH (CH<sub>3</sub>) O-)<sub>6</sub>] (Me) (EtO) Si (CH<sub>2</sub>)<sub>3</sub>SH, [(XO- (CH<sub>2</sub>-CH (CH<sub>3</sub>) O-)<sub>7</sub>] (Me) (EtO) Si (CH<sub>2</sub>) <sub>3</sub>SH, [(XO- (CH<sub>2</sub>-CH (CH<sub>3</sub>) O-) <sub>8</sub>] (Me) (EtO) Si (CH<sub>2</sub>) <sub>3</sub>SH, [(XO- (CH<sub>2</sub>-CH (CH<sub>3</sub>) O-) <sub>9</sub>] (Me) (EtO) Si (CH<sub>2</sub>) <sub>3</sub>SH, [(XO- (CH<sub>2</sub>-CH (CH<sub>3</sub>) O-) <sub>10</sub>] (Me) (EtO) Si (CH<sub>2</sub>) <sub>3</sub>SH, [(XO- (CH<sub>2</sub>-CH (CH<sub>3</sub>) O-) <sub>11</sub>] (Me) (EtO) Si (CH<sub>2</sub>) <sub>3</sub>SH, [(XO- (CH<sub>2</sub>-CH (CH<sub>3</sub>) O-)<sub>12</sub>] (Me) (EtO) Si (CH<sub>2</sub>) <sub>3</sub>SH, [(XO- (CH<sub>2</sub>-CH (CH<sub>3</sub>)O-)<sub>13</sub>] (Me) (EtO) Si (CH<sub>2</sub>)<sub>3</sub>SH, [(XO- (CH<sub>2</sub>-CH (CH<sub>3</sub>)O-)<sub>14</sub>] (Me) (EtO) Si (CH<sub>2</sub>)<sub>3</sub>SH, [(XO- (CH<sub>2</sub>-CH (CH<sub>3</sub>)O-)<sub>15</sub>] (Me) (EtO) Si (CH<sub>2</sub>)<sub>3</sub>SH, [(XO- (CH<sub>2</sub>-CH (CH<sub>3</sub>)O-)<sub>16</sub>] (Me) (EtO) Si (CH<sub>2</sub>)<sub>3</sub>SH, [(XO- (CH<sub>2</sub>-CH (CH<sub>3</sub>)O-)<sub>17</sub>] (Me) (EtO) Si (CH<sub>2</sub>)<sub>3</sub>SH, [(XO- (CH<sub>2</sub>-CH (CH<sub>3</sub>)O-)<sub>18</sub>] (Me) (EtO) Si (CH<sub>2</sub>)<sub>3</sub>SH, [(XO- (CH<sub>2</sub>-CH (CH<sub>3</sub>)O-)<sub>19</sub>] (Me) (EtO) Si (CH<sub>2</sub>)<sub>3</sub>SH, [(XO- (CH<sub>2</sub>-CH (CH<sub>3</sub>)O-)<sub>20</sub>] (Me) (EtO) Si (CH<sub>2</sub>)<sub>3</sub>SH, [(XO- (CH<sub>2</sub>-CH (CH<sub>3</sub>)O-)<sub>19</sub>] (Me) (EtO) Si (CH<sub>2</sub>)<sub>3</sub>SH, [(XO- (CH<sub>2</sub>-CH (CH<sub>3</sub>)O-)<sub>20</sub>] (Me) (EtO) Si (CH<sub>2</sub>)<sub>3</sub>SH, [(XO- (CH<sub>2</sub>-CH (CH<sub>3</sub>) O-)<sub>2</sub>]<sub>2</sub> (Me) Si (CH<sub>2</sub>) <sub>3</sub>SH, [(XO- (CH<sub>2</sub>-CH (CH<sub>3</sub>) O-)<sub>3</sub>]<sub>2</sub> (Me) Si (CH<sub>2</sub>) <sub>3</sub>SH, [(XO- (CH<sub>2</sub>-CH (CH<sub>3</sub>) O-)<sub>4</sub>]<sub>2</sub> (Me) Si (CH<sub>2</sub>) <sub>3</sub>SH, [(XO- (CH<sub>2</sub>-CH (CH<sub>3</sub>)O-)<sub>5</sub>]<sub>2</sub> (Me) Si (CH<sub>2</sub>)<sub>3</sub>SH, [(X-0- (CH<sub>2</sub>-CH (CH<sub>3</sub>)O-)<sub>6</sub>]<sub>2</sub> (Me) Si (CH<sub>2</sub>) <sub>3</sub>SH, [(X-0- (CH<sub>2</sub>-CH (CH<sub>3</sub>)O-)<sub>7</sub>]<sub>2</sub> (Me) Si (CH<sub>2</sub>) <sub>3</sub>SH, [(X-0- (CH<sub>2</sub>-CH (CH<sub>3</sub>)O-)<sub>8</sub>] <sub>2</sub> (Me) Si (CH<sub>2</sub>) <sub>3</sub>SH, [(X-0- (CH<sub>2</sub>-CH (CH<sub>3</sub>) O-)<sub>9</sub>] <sub>2</sub> (Me) Si (CH<sub>2</sub>) <sub>3</sub>SH, [(XO- (CH<sub>2</sub>-CH (CH<sub>3</sub>) O-)<sub>10</sub>]<sub>2</sub> (Me) Si (CH<sub>2</sub>) <sub>3</sub>SH, [(XO- (CH<sub>2</sub>-CH (CH<sub>3</sub>) O-)<sub>11</sub>]<sub>2</sub> (Me) Si (CH<sub>2</sub>) <sub>3</sub>SH, [(XO- (CH<sub>2</sub>-CH (CH<sub>3</sub>)O-)<sub>12</sub>]<sub>2</sub>(Me) Si (CH<sub>2</sub>)<sub>3</sub>SH, [(XO- (CH<sub>2</sub>-CH (CH<sub>3</sub>)O-)<sub>13</sub>]<sub>2</sub>(Me) Si (CH<sub>2</sub>)<sub>3</sub>SH, [(XO- (CH<sub>2</sub>-CH (CH<sub>3</sub>)O-)<sub>14</sub>]<sub>2</sub>(Me) Si (CH<sub>2</sub>)<sub>3</sub>SH, [(XO- (CH<sub>2</sub>-CH (CH<sub>3</sub>)O-)<sub>15</sub>]<sub>2</sub>(Me) Si (CH<sub>2</sub>)<sub>3</sub>SH, [(X-0- (CH<sub>2</sub>-CH (CH<sub>3</sub>)O-)<sub>16</sub>]<sub>2</sub>(Me) Si (CH<sub>2</sub>)<sub>3</sub>SH, [(X-0- (CH<sub>2</sub>-CH (CH<sub>3</sub>)O-)<sub>17</sub>]<sub>2</sub>(Me) Si (CH<sub>2</sub>)<sub>3</sub>SH, [(XO- (CH<sub>2</sub>-CH (CH<sub>3</sub>)O-)<sub>18</sub>]<sub>2</sub>(Me) Si (CH<sub>2</sub>)<sub>3</sub>SH, [(X-0- (CH<sub>2</sub>-CH (CH<sub>3</sub>)O-)<sub>19</sub>]<sub>2</sub>(Me) Si (CH<sub>2</sub>)<sub>3</sub>SH, [(X-0- (CH<sub>2</sub>-CH (CH<sub>3</sub>)O-)<sub>20</sub>]<sub>2</sub>(Me) Si (CH<sub>2</sub>)<sub>3</sub>SH, [(XO- (CH<sub>2</sub>-CH (CH<sub>3</sub>)O-)<sub>2</sub>] (Me)<sub>2</sub>Themselves<sub>2</sub>)<sub>3</sub>SH, [(XO- (CH<sub>2</sub>-CH (CH<sub>3</sub>)O-)<sub>3</sub>] (Me) <sub>2</sub>Themselves<sub>2</sub>)<sub>3</sub>SH, [(XO- (CH<sub>2</sub>-CH (CH<sub>3</sub>)O-)<sub>4</sub>] (Me) <sub>2</sub>Themselves<sub>2</sub>)<sub>3</sub>SH, [(XO- (CH<sub>2</sub>-CH (CH<sub>3</sub>)O-)<sub>5</sub>] (Me) <sub>2</sub>Themselves<sub>2</sub>)<sub>3</sub>SH, [(XO- (CH<sub>2</sub>-CH (CH<sub>3</sub>)O-)<sub>6</sub>] (Me) <sub>2</sub>Themselves<sub>2</sub>)<sub>3</sub>SH, [(X-0- (CH<sub>2</sub>-CH (CH<sub>3</sub>)O-)<sub>7</sub>] (Me) <sub>2</sub>Themselves<sub>2</sub>)<sub>3</sub>SH, [(XO- (CH<sub>2</sub>-CH (CH<sub>3</sub>)O-)<sub>8</sub>] (Me)<sub>2</sub>Themselves<sub>2</sub>)<sub>3</sub>SH, [(XO- (CH<sub>2</sub>-CH (CH<sub>3</sub>)O-)<sub>9</sub>] (Me)<sub>2</sub>Themselves<sub>2</sub>)<sub>3</sub>SH, [(XO- (CH<sub>2</sub>-CH (CH<sub>3</sub>) O-)<sub>10</sub>] (Me)<sub>2</sub>Themselves<sub>2</sub>)<sub>3</sub>SH, [(XO- (CH<sub>2</sub>-CH (CH<sub>3</sub>)O-)<sub>11</sub>] (Me)<sub>2</sub>Themselves<sub>2</sub>)<sub>3</sub>SH, [(XO- (CH<sub>2</sub>-CH (CH<sub>3</sub>)O-)<sub>12</sub>] (Me)<sub>2</sub>Themselves<sub>2</sub>)<sub>3</sub>SH, [(XO- (CH<sub>2</sub>-CH (CH<sub>3</sub>)O-)<sub>13</sub>] (Me)<sub>2</sub>Themselves<sub>2</sub>)<sub>3</sub>SH, [(XO- (CH<sub>2</sub>-CH (CH<sub>3</sub>)O-)<sub>14</sub>] (Me)<sub>2</sub>Themselves<sub>2</sub>)<sub>3</sub>SH, [(XO- (CH<sub>2</sub>-CH (CH<sub>3</sub>)O-)<sub>15</sub>] (Me)<sub>2</sub>Themselves<sub>2</sub>)<sub>3</sub>SH, [(XO- (CH<sub>2</sub>-CH (CH<sub>3</sub>)O-)<sub>16</sub>] (Me)<sub>2</sub>Themselves<sub>2</sub>)<sub>3</sub>SH, [(XO- (CH<sub>2</sub>-CH (CH<sub>3</sub>)O-)<sub>17</sub>] (Me)<sub>2</sub>Themselves<sub>2</sub>)<sub>3</sub>SH, [(XO- (CH<sub>2</sub>-CH (CH<sub>3</sub>)O-)<sub>18</sub>] (Me)<sub>2</sub>Themselves<sub>2</sub>)<sub>3</sub>SH, [(XO- (CH<sub>2</sub>-CH (CH<sub>3</sub>)O-)<sub>19</sub>] (Me)<sub>2</sub>Themselves<sub>2</sub>)<sub>3</sub>SH or [(XO- (CH<sub>2</sub>-CH (CH<sub>3</sub>)O-)<sub>20</sub>] (Me)<sub>2</sub>Themselves<sub>2</sub>)<sub>3</sub>SH.
The organosilane of the general formula I can consist of a mixture of compounds of organosilanes of the general formula I. The mixtures can contain compounds of organosilanes with the same or different m. The mixtures of organosilanes can contain compounds with the same or different Y groups. The mixtures can be compounds of organosilanes with the same or different R<sup>1</sup>-, R<sup>2</sup>-, R<sup>3</sup>- or R<sup>4</sup>Groups included.
Condensation products, that is to say oligo- and polysiloxanes, can be formed from the organosilanes of the general formula I by adding water. The oligosiloxanes and polysiloxanes can be obtained by oligomerization or cooligomerization of the corresponding alkoxysilane compounds of the general formula I by adding water and adding additives and procedures known to those skilled in the art. The resulting oligo or Polymerization products can be contained in the organosilane compounds of the general formula I.
The organosilane of the general formula I can also be an oligo- or polymerization product of the organosilane compound of the general formula I. The organosilane of the general formula I can be a mixture of oligo- or polymerization products of the organosilane compound of the general formula I and uncondensed organosilane compound of the general formula I.
The organosilane of the general formula I can be added to the mixing process either in pure form or in the form of an inert organic or inorganic carrier, and also pre-reacted with an organic or inorganic carrier. Preferred carrier materials can be precipitated or pyrogenic silicas, waxes, thermoplastics, natural or synthetic silicates, natural or synthetic oxides, especially aluminum oxide, or carbon blacks. Furthermore, the organosilanes of the general formula I can also be added to the mixing process prereacted with the filler to be used.
The following fillers can be used as fillers for the rubber mixtures according to the invention:<ul id="ul0001" list-style="dash"><li>Carbon blacks: The carbon blacks to be used here are produced using the flame black, furnace, gas black or thermal process and have BET surfaces of 20 to 200 m<sup>2</sup>/G. The carbon blacks can optionally also contain heteroatoms, such as Si.</li><li>Amorphous silicas, produced for example by precipitation of solutions of silicates or flame hydrolysis of silicon halides with specific surfaces from 5 to 1000 m<sup>2</sup>/ g, preferably 20 to 400 m<sup>2</sup>/ g (BET surface area) and with primary particle sizes of 10 to 400 nm. The silicas can optionally also be present as mixed oxides with other metal oxides, such as Al, Mg, Ca, Ba, Zn and titanium oxides.</li><li>Synthetic silicates, such as aluminum silicate, alkaline earth silicates, such as magnesium silicate or calcium silicate, with BET surfaces of 20 to 400 m<sup>2</sup>/ g and primary particle diameters from 10 to 400 nm.</li><li>Synthetic or natural aluminum oxides and hydroxides.</li><li>Natural silicates, such as kaolin and other naturally occurring silicas.</li><li>Glass fiber and glass fiber products (mats, strands) or micro glass balls.</li></ul>
Amorphous silicas, produced by precipitation of solutions of silicates with BET surface areas of 20 to 400 m, can preferably be used<sup>2</sup>/ g in amounts of 5 to 150 parts by weight, based in each case on 100 parts of rubber.
In addition to natural rubber, synthetic rubbers can also be used to produce the rubber mixtures according to the invention. Preferred synthetic rubbers are described, for example, by W. Hofmann, Kautschuktechnologie, Genter Verlag, Stuttgart 1980. They include, among others<ul id="ul0002" list-style="dash"><li>Polybutadiene (BR),</li><li>Polyisoprene (IR),</li><li>Styrene / butadiene copolymers, for example emulsion SBR (E-SBR) or solution SBR (L-SBR), preferably with styrene contents of 1 to 60, particularly preferably 5 to 50% by weight (SBR),</li><li>Chloroprene (CR),</li><li>Isobutylene / isoprene copolymers (IIR),</li><li>Butadiene / acrylonitrile copolymers with acrylonitrile contents of 5 to 60, preferably 10 to 50% by weight (NBR),</li><li>partially hydrogenated or fully hydrogenated NBR rubber (HNBR),</li><li>Ethylene / propylene / diene copolymers (EPDM),</li><li>abovementioned rubbers which additionally have functional groups, such as, for example, carboxy, silanol or epoxy groups, for example epoxidized NR, carboxy-functionalized NBR or silanol- (-SiOH) or siloxy-functionalized (-Si-OR) SBR,</li></ul>as well as mixtures of these rubbers. Anionically polymerized L-SBR rubbers (solution SBR) with a glass transition temperature above -50 ° C. and mixtures thereof with diene rubbers can be used in particular for the production of car tire treads.
The raw rubber mixtures and vulcanizates according to the invention can contain further rubber auxiliaries, such as reaction accelerators, anti-aging agents, heat stabilizers, light stabilizers, ozone preservatives, processing aids, plasticizers, tackifiers, blowing agents, dyes, pigments, waxes, extenders, organic acids, retarders, metal oxides or activators, such as triethanolamine , contain.
Other rubber auxiliaries can be polyalkylene glycols. Polyalkylene glycols can be polyethylene glycols, polypropylene glycols and / or polybutylene glycols.
The polyalkylene glycols can have a molecular weight between 50 and 50,000 g / mol, preferably between 50 and 20,000 g / mol, particularly preferably between 200 and 10,000 g / mol, very particularly preferably between 400 and 6,000 g / mol, extremely preferably between 500 and 3,000 g / mol.
The polyethylene glycols can be hydrocarbon-terminated polyethylene glycol Alk-0- (CH<sub>2</sub>-CH<sub>2</sub>-O)<sub>yI</sub>-H or Alk- (CH<sub>2</sub>-CH<sub>2</sub>-O)<sub>yI</sub>-Alk be with y<sup>I.</sup> = 2-25, preferably y<sup>I.</sup> = 2-15, particularly preferably y<sup>I.</sup> = 3-8 and 10-14, very particularly preferably y<sup>I.</sup> = 3-6 and 10-13, and Alk is a branched or unbranched, unsubstituted or substituted, saturated or unsaturated hydrocarbon with 1 to 35, preferably 4 to 25, particularly preferably 6 to 20, very particularly preferably 10 to 20, extremely preferred 11 to 14, carbon atoms.
The polypropylene glycols can be hydrocarbon-terminated polypropylene glycol Alk-0- (CH<sub>2</sub>-CH (CH<sub>3</sub>) -0) y<sub>I.</sub>-H or Alk-0- (CH<sub>2</sub>-CH (CH<sub>3</sub>) -0) y<sub>I.</sub>-Alk, where y<sup>I.</sup> and Alk have the meaning given above.
The polybutylene glycols can be hydrocarbon-terminated polybutylene glycol Alk-0- (CH<sub>2</sub>-CH<sub>2</sub>-CH<sub>2</sub>-CH<sub>2</sub>-O)<sub>yI</sub>-H, Alk-O- (CH<sub>2</sub>-CH (CH<sub>3</sub>) -CH<sub>2</sub>-O)<sub>yI</sub>-H, Alk-O- (CH<sub>2</sub>-CH<sub>2</sub>-CH<sub>2</sub>-CH<sub>2</sub>-O)<sub>yI</sub>-Alk or Alk-O- (CH<sub>2</sub>-CH (CH<sub>3</sub>) -CH<sub>2</sub>-O)<sub>yI</sub>-Alk, where y<sup>I.</sup> and Alk have the meaning given above.
Polyalkylene glycols can be polyethylene glycol, polypropylene glycol, polybutylene glycol, or neopentyl glycol HO-CH etherified with mixtures thereof<sub>2-</sub>C (Me)<sub>2</sub>-CH<sub>2</sub>-OH, pentaerythritol C (CH<sub>2</sub>-OH)<sub>4</sub> or trimethylolpropane CH<sub>3</sub>-CH<sub>2</sub>-C (CH<sub>2</sub>-OH)<sub>3</sub>, where the repeating units of ethylene glycol, propylene glycol and / or butylene glycol in the etherified polyalcohols are between 2 and 100, preferably between 2 and 50, particularly preferably between 3 and 30, very particularly preferably between 3 and 15.
The rubber auxiliaries can be used in known amounts, which depend inter alia on the intended use. Usual amounts are, for example, amounts of 0.1 to 50% by weight, preferably 0.1 to 30% by weight, based on rubber. Sulfur or sulfur-donating substances can be used as crosslinking agents. The rubber mixtures according to the invention can also contain vulcanization accelerators. For example, mercaptobenzothiazoles, sulfenamides, guanidines, thiurams, dithiocarbamates, thioureas and thiocarbonates can be used as suitable vulcanization accelerators. The vulcanization accelerators and sulfur can be used in amounts of 0.1 to 10% by weight, preferably 0.1 to 5% by weight, based on rubber.
The invention further relates to a process for the preparation of the rubber mixture according to the invention, which is characterized in that the rubber, filler, optionally further rubber auxiliaries and at least one organosilane of the general formula I are mixed.
The vulcanization of the rubber mixtures according to the invention can take place at temperatures from 100 to 200 ° C., preferably 130 to 180 ° C., if appropriate under pressure from 10 to 200 bar. The blending of the rubbers with the filler, optionally rubber auxiliaries and the organosilane of the general formula I can be carried out in known mixing units, such as rollers, internal mixers and mixing extruders.
The rubber mixtures according to the invention can be used for the production of moldings, for example for the production of pneumatic tires, tire treads, cable jackets, tubes, drive belts, conveyor belts, roller coverings, tires, shoe soles, sealing rings and damping elements.
The rubber mixtures according to the invention show an improved tear resistance.
Examples:
Example 1: 3-Mercaptopropyl (dimethylethoxysilane) (MPDMES)
37.5 g of dried NaSH and 600 ml of dry ethanol are placed in an autoclave with a double glass jacket and Hastelloy C22 lid + fittings (Buechi AG) at room temperature. The suspension is heated and stirred at 50 ° C for 20 min. A mixture of 100 g of 3-chloropropyl (dimethylethoxysilane) and 5 g of 3-chloropropyl (dimethylchlorosilane) is added to the suspension with a pressure burette. A further 200 ml of ethanol are added to the mixture and heated to 93-96 ° C. with stirring. The temperature is held for 180 min. The mixture is then cooled to room temperature.
The resulting suspension is filtered and the filter cake is washed with toluene. The filtrate is freed from the solvent on a rotary evaporator. The suspension obtained is filtered, the filter cake is washed with toluene and the filtrate is freed again from the toluene on a rotary evaporator.
88.3 g of liquid, colorless product are obtained.
Comparative example
1:
[(EtO) Me
2
Themselves
2
-CH
2
-CH
2
-]
2
S
3,66
700 ml of ethanol with 337 g of dried Na are placed in a 2000 ml four-necked flask<sub>2</sub>S<sub>4</sub> Weighed (1.94 mol) and 700 g of 3-chloropropyl (dimethylethoxysilane) (3.88 mol) and heated to boiling with stirring. The reaction solution is boiled under reflux for 270 min. 3 g of 3-chloropropyl (dimethylethoxysilane) are added to the suspension and the mixture is heated to reflux for a further 30 min.
The suspension is cooled, filtered and the residue washed with ethanol. The filtrate is freed from the solvent on a rotary evaporator at 20-400 mbar and 60-90 ° C. and filtered again. 769.2 g of an orange liquid are isolated.
Analytics:
1.
1
H-NMR
<tables id="tabl0001" num="0001"><table frame="all"><tgroup cols="4" colsep="1" rowsep="1"><colspec colnum="1" colname="col1" colwidth="55mm" colsep="1" /><colspec colnum="2" colname="col2" colwidth="37mm" colsep="1" /><colspec colnum="3" colname="col3" colwidth="14mm" colsep="1" /><colspec colnum="4" colname="col4" colwidth="14mm" colsep="1" /><thead><row><entry namest="col1" nameend="col1" rowsep="0" align="center" valign="top">Content of</entry><entry namest="col2" nameend="col4" colsep="1" rowsep="1" align="center" valign="top">Content of [(EtO) Me<sub>2</sub>Themselves<sub>2</sub>-CH<sub>2</sub>-CH<sub>2</sub>-]<sub>2</sub>S<sub>x</sub></entry></row><row><entry namest="col1" nameend="col1" align="center" valign="top">3-chloropropyl (dimethylethoxysilane)</entry><entry namest="col2" nameend="col2" align="center" valign="top">x = 2</entry><entry namest="col3" nameend="col3" align="center" valign="top">x = 3</entry><entry namest="col4" nameend="col4" align="center" valign="top">x = 4</entry></row></thead><tbody><row><entry namest="col1" nameend="col1" align="center" valign="top">mol .-%</entry><entry namest="col2" nameend="col2" align="center" valign="top">mol%</entry><entry namest="col3" nameend="col3" align="center" valign="top">mol%</entry><entry namest="col4" nameend="col4" align="center" valign="top">mol%</entry></row><row><entry namest="col1" nameend="col1" align="center" valign="top">2,8</entry><entry namest="col2" nameend="col2" align="center" valign="top">17,1</entry><entry namest="col3" nameend="col3" align="center" valign="top">28,0</entry><entry namest="col4" nameend="col4" align="center" valign="top">25,2</entry></row></tbody></tgroup></table></tables>
The mean chain length -S<sub>x</sub>-, based on the NMR data (p<sub>1</sub>-S<sub>10</sub>), is 3.66.
2.
29
Si NMR
Comparative example 1 contains 1.6 mol% of dimerized [(EtO) Me<sub>2</sub>Themselves<sub>2</sub>-CH<sub>2</sub>-CH<sub>2</sub>]<sub>2</sub>S<sub>x</sub>.
A DRX 500 NMR device from Bruker is used for the analysis of the comparison product in accordance with the rules and operating instructions known to the person skilled in the art. The measuring frequencies are 99.35 MHz for<sup>29</sup>Si cores and 500.13 MHz for <sup>1</sup>H-cores. Tetramethylsilane (TMS) serves as a reference.
The analysis of bis (alkoxysilylorganyl) polysulfides and mercaptoorganyl (alkoxysilanes) and their mixtures is described, for example, in U. Görl, J. Munzenberg, D. Luginsland, A. Müller Kautschuk Gummi Kunststoffe 1999, 52 (9), 588ff, D. Luginsland Kautschuk Gummi Kunststoffe 2000, 53 (1-2), 10ff or MW Backer et al, <i>Polymer preprints</i> 2003, 44 (1), 245ff.
Example 2: Rubber-technical investigations
The formulation used for the rubber compounds is given in Table 1 below. The unit phr means parts by weight, based on 100 parts of the raw rubber used. The silanes according to the invention are dosed with the same weight. The general process for the production of rubber mixtures and their vulcanizates is described in the book: "Rubber Technology Handbook", W. Hofmann, Hanser Verlag 1994.
The coupling reagents Si 69, a bis (triethoxysilylpropyl) tetrasulfide (TESPT), and VP Si 263, a 3-mercaptopropyl (triethoxysilane) (MPTES), are sales products of Degussa AG. The coupling reagent VP Si 208, an octylsilyltriethoxysilane, is an processing aid as alkylsilane and is a sales product of Degussa AG.<tables id="tabl0002" num="0002"><table frame="all"><title>Table 1:</title><tgroup cols="5" colsep="0" rowsep="1"><colspec colnum="1" colname="col1" colwidth="63mm" colsep="0" /><colspec colnum="2" colname="col2" colwidth="26mm" colsep="0" /><colspec colnum="3" colname="col3" colwidth="26mm" colsep="0" /><colspec colnum="4" colname="col4" colwidth="26mm" colsep="0" /><colspec colnum="5" colname="col5" colwidth="21mm" colsep="1" /><thead><row rowsep="0"><entry namest="col1" nameend="col1" morerows="1" rowsep="1" align="left" valign="top">substance</entry><entry namest="col2" nameend="col2" align="left" valign="top">Mix 1</entry><entry namest="col3" nameend="col3" align="left" valign="top">Mix 2</entry><entry namest="col4" nameend="col4" align="left" valign="top">Mix 3</entry><entry namest="col5" nameend="col5" align="left" valign="top">Mix 4</entry></row><row><entry namest="col2" nameend="col2" align="left" valign="top">Reference [phr]</entry><entry namest="col3" nameend="col3" align="left" valign="top">Reference [phr]</entry><entry namest="col4" nameend="col4" align="left" valign="top">Reference [phr]</entry><entry namest="col5" nameend="col5" align="left" valign="top">[phr]</entry></row></thead><tbody><row><entry namest="col1" nameend="col5" colsep="1" align="left" valign="top"><b>1. step</b></entry></row><row rowsep="0"><entry namest="col1" nameend="col1" align="left" valign="top">Buna VSL 5025-1</entry><entry namest="col2" nameend="col2" align="left" valign="top">96</entry><entry namest="col3" nameend="col3" align="left" valign="top">96</entry><entry namest="col4" nameend="col4" align="left" valign="top">96</entry><entry namest="col5" nameend="col5" align="left" valign="top">96</entry></row><row rowsep="0"><entry namest="col1" nameend="col1" align="left" valign="top">Buna CB 24</entry><entry namest="col2" nameend="col2" align="left" valign="top">30</entry><entry namest="col3" nameend="col3" align="left" valign="top">30</entry><entry namest="col4" nameend="col4" align="left" valign="top">30</entry><entry namest="col5" nameend="col5" align="left" valign="top">30</entry></row><row rowsep="0"><entry namest="col1" nameend="col1" align="left" valign="top">Ultrasil 7000 GR</entry><entry namest="col2" nameend="col2" align="left" valign="top">80</entry><entry namest="col3" nameend="col3" align="left" valign="top">80</entry><entry namest="col4" nameend="col4" align="left" valign="top">80</entry><entry namest="col5" nameend="col5" align="left" valign="top">80</entry></row><row rowsep="0"><entry namest="col1" nameend="col1" align="left" valign="top">Si 69 (TESPT)</entry><entry namest="col2" nameend="col2" align="left" valign="top">2</entry><entry namest="col3" nameend="col3" align="left" valign="top">-</entry><entry namest="col4" nameend="col4" align="left" valign="top">-</entry><entry namest="col5" nameend="col5" align="left" valign="top">-</entry></row><row rowsep="0"><entry namest="col1" nameend="col1" align="left" valign="top">VP Si 263 (MPTES)</entry><entry namest="col2" nameend="col2" align="left" valign="top">-</entry><entry namest="col3" nameend="col3" align="left" valign="top">2</entry><entry namest="col4" nameend="col4" align="left" valign="top">-</entry><entry namest="col5" nameend="col5" align="left" valign="top">-</entry></row><row rowsep="0"><entry namest="col1" nameend="col1" align="left" valign="top">Silane from Comparative Example 1 (DMESPT)</entry><entry namest="col2" nameend="col2" align="left" valign="top">-</entry><entry namest="col3" nameend="col3" align="left" valign="top">-</entry><entry namest="col4" nameend="col4" align="left" valign="top">2</entry><entry namest="col5" nameend="col5" align="left" valign="top">-</entry></row><row rowsep="0"><entry namest="col1" nameend="col1" align="left" valign="top">Silane from Example 1 (MPDMES)</entry><entry namest="col2" nameend="col2" align="left" valign="top">-</entry><entry namest="col3" nameend="col3" align="left" valign="top">-</entry><entry namest="col4" nameend="col4" align="left" valign="top">-</entry><entry namest="col5" nameend="col5" align="left" valign="top">2</entry></row><row rowsep="0"><entry namest="col1" nameend="col1" align="left" valign="top">VP Si 208</entry><entry namest="col2" nameend="col2" align="left" valign="top">2,5</entry><entry namest="col3" nameend="col3" align="left" valign="top">2,5</entry><entry namest="col4" nameend="col4" align="left" valign="top">2,5</entry><entry namest="col5" nameend="col5" align="left" valign="top">2,5</entry></row><row rowsep="0"><entry namest="col1" nameend="col1" align="left" valign="top">ZnO</entry><entry namest="col2" nameend="col2" align="left" valign="top">3</entry><entry namest="col3" nameend="col3" align="left" valign="top">3</entry><entry namest="col4" nameend="col4" align="left" valign="top">3</entry><entry namest="col5" nameend="col5" align="left" valign="top">3</entry></row><row rowsep="0"><entry namest="col1" nameend="col1" align="left" valign="top">Stearic acid</entry><entry namest="col2" nameend="col2" align="left" valign="top">2</entry><entry namest="col3" nameend="col3" align="left" valign="top">2</entry><entry namest="col4" nameend="col4" align="left" valign="top">2</entry><entry namest="col5" nameend="col5" align="left" valign="top">2</entry></row><row rowsep="0"><entry namest="col1" nameend="col1" align="left" valign="top">Naftolen ZD</entry><entry namest="col2" nameend="col2" align="left" valign="top">10</entry><entry namest="col3" nameend="col3" align="left" valign="top">10</entry><entry namest="col4" nameend="col4" align="left" valign="top">10</entry><entry namest="col5" nameend="col5" align="left" valign="top">10</entry></row><row rowsep="0"><entry namest="col1" nameend="col1" align="left" valign="top">Vulkanox 4020</entry><entry namest="col2" nameend="col2" align="left" valign="top">1,5</entry><entry namest="col3" nameend="col3" align="left" valign="top">1,5</entry><entry namest="col4" nameend="col4" align="left" valign="top">1,5</entry><entry namest="col5" nameend="col5" align="left" valign="top">1,5</entry></row><row rowsep="0"><entry namest="col1" nameend="col1" align="left" valign="top">Protector G 3108</entry><entry namest="col2" nameend="col2" align="left" valign="top">1</entry><entry namest="col3" nameend="col3" align="left" valign="top">1</entry><entry namest="col4" nameend="col4" align="left" valign="top">1</entry><entry namest="col5" nameend="col5" align="left" valign="top">1</entry></row><row><entry namest="col1" nameend="col1" align="left" valign="top"><b>2nd step</b></entry><entry namest="col2" nameend="col2" align="left" valign="top" /><entry namest="col3" nameend="col3" align="left" valign="top" /><entry namest="col4" nameend="col4" align="left" valign="top" /><entry namest="col5" nameend="col5" align="left" valign="top" /></row><row><entry namest="col1" nameend="col5" colsep="1" rowsep="1" align="left" valign="top">Batch level 1</entry></row><row><entry namest="col1" nameend="col5" colsep="1" rowsep="1" align="left" valign="top"><b>3rd step</b></entry></row><row rowsep="0"><entry namest="col1" nameend="col1" align="left" valign="top">Batch level 2</entry><entry namest="col2" nameend="col2" align="left" valign="top" /><entry namest="col3" nameend="col3" align="left" valign="top" /><entry namest="col4" nameend="col4" align="left" valign="top" /><entry namest="col5" nameend="col5" align="left" valign="top" /></row><row rowsep="0"><entry namest="col1" nameend="col1" align="left" valign="top">Vulkacit D</entry><entry namest="col2" nameend="col2" align="left" valign="top">2</entry><entry namest="col3" nameend="col3" align="left" valign="top">2</entry><entry namest="col4" nameend="col4" align="left" valign="top">2</entry><entry namest="col5" nameend="col5" align="left" valign="top">2</entry></row><row rowsep="0"><entry namest="col1" nameend="col1" align="left" valign="top">Vulkacit CZ</entry><entry namest="col2" nameend="col2" align="left" valign="top">1,5</entry><entry namest="col3" nameend="col3" align="left" valign="top">1,5</entry><entry namest="col4" nameend="col4" align="left" valign="top">1,5</entry><entry namest="col5" nameend="col5" align="left" valign="top">1,5</entry></row><row><entry namest="col1" nameend="col1" align="left" valign="top">Perkacit TBzTD</entry><entry namest="col2" nameend="col2" align="left" valign="top">0,2</entry><entry namest="col3" nameend="col3" align="left" valign="top">0,2</entry><entry namest="col4" nameend="col4" align="left" valign="top">0,2</entry><entry namest="col5" nameend="col5" align="left" valign="top">0,2</entry></row><row><entry namest="col1" nameend="col1" align="left" valign="top">sulfur</entry><entry namest="col2" nameend="col2" align="left" valign="top">1,5</entry><entry namest="col3" nameend="col3" align="left" valign="top">1,5</entry><entry namest="col4" nameend="col4" align="left" valign="top">1,5</entry><entry namest="col5" nameend="col5" align="left" valign="top">1,5</entry></row></tbody></tgroup></table></tables>
The polymer VSL 5025-1 is an SBR copolymer from Bayer AG polymerized in solution, with a styrene content of 25% by weight and a butadiene content of 75% by weight. The copolymer contains 37.5 phr oil and has a Mooney viscosity (ML 1 + 4/100 ° C) of 50.
The polymer Buna CB 24 is a cis 1,4-polybutadiene (neodymium type) from Bayer AG, with a cis 1,4 content of at least 96% and a Mooney viscosity of 44 ± 5.
Ultrasil 7000 GR is an easily dispersible silica from Degussa AG and has a BET surface area of 170 m<sup>2</sup>/G.
Naftolen ZD from Chemetall is used as the aromatic oil, Vulkanox 4020 is PPD from Bayer AG and Protektor G3108 is an ozone protection wax from Paramelt BV. Vulkacit D (DPG) and Vulkacit CZ (CBS) are commercial products from Bayer AG. Perkacit TBzTD (Tetrabenzylthiuramtetrasulfid) is a product of Flexsys NV.
The rubber mixtures are produced in an internal mixer in accordance with the mixing instructions in Table 2.<tables id="tabl0003" num="0003"><table frame="all"><title>Table 2:</title><tgroup cols="3" colsep="1" rowsep="1"><colspec colnum="1" colname="col1" colwidth="16mm" colsep="0" /><colspec colnum="2" colname="col2" colwidth="16mm" colsep="1" /><colspec colnum="3" colname="col3" colwidth="134mm" colsep="1" /><thead><row><entry namest="col1" nameend="col3" colsep="1" rowsep="1" align="center" valign="top">step 1</entry></row><row><entry namest="col1" nameend="col2" colsep="1" rowsep="1" align="left" valign="top">Settings</entry><entry namest="col3" nameend="col3" align="left" valign="top" /></row></thead><tbody><row rowsep="0"><entry namest="col1" nameend="col2" colsep="1" rowsep="0" align="left" valign="top">Mixing unit</entry><entry namest="col3" nameend="col3" align="left" valign="top">Werner & Pfleiderer E-type</entry></row><row rowsep="0"><entry namest="col1" nameend="col2" colsep="1" rowsep="0" align="left" valign="top">rotational speed</entry><entry namest="col3" nameend="col3" align="left" valign="top">60 min<sup>-1</sup></entry></row><row rowsep="0"><entry namest="col1" nameend="col2" colsep="1" rowsep="0" align="left" valign="top">Stamp printing</entry><entry namest="col3" nameend="col3" align="left" valign="top">5.5 bar</entry></row><row rowsep="0"><entry namest="col1" nameend="col2" colsep="1" rowsep="0" align="left" valign="top">Empty volume</entry><entry namest="col3" nameend="col3" align="left" valign="top">1.58 L.</entry></row><row rowsep="0"><entry namest="col1" nameend="col2" colsep="1" rowsep="0" align="left" valign="top">Degree of filling</entry><entry namest="col3" nameend="col3" align="left" valign="top">0,56</entry></row><row><entry namest="col1" nameend="col2" colsep="1" rowsep="1" align="left" valign="top">Flow temp.</entry><entry namest="col3" nameend="col3" align="left" valign="top">70 ° C</entry></row></tbody></tgroup><tgroup cols="3" colsep="1" rowsep="1"><colspec colnum="1" colname="col1" colwidth="16mm" colsep="0" /><colspec colnum="2" colname="col2" colwidth="16mm" colsep="1" /><colspec colnum="3" colname="col3" colwidth="134mm" colsep="1" /><thead><row><entry namest="col1" nameend="col2" colsep="1" rowsep="1" align="left" valign="top">Mixing process</entry><entry namest="col3" nameend="col3" align="left" valign="top" /></row></thead><tbody><row rowsep="0"><entry namest="col1" nameend="col1" align="left" valign="top">0 to</entry><entry namest="col2" nameend="col2" align="left" valign="top">1 min</entry><entry namest="col3" nameend="col3" align="left" valign="top">Buna VSL 5025-1 + Buna CB 24</entry></row><row rowsep="0"><entry namest="col1" nameend="col1" align="left" valign="top">1 to</entry><entry namest="col2" nameend="col2" align="left" valign="top">2nd min</entry><entry namest="col3" nameend="col3" align="left" valign="top">1/2 silica, ZnO, stearic acid, Naftolen ZD, silane</entry></row><row rowsep="0"><entry namest="col1" nameend="col1" align="left" valign="top">2nd to</entry><entry namest="col2" nameend="col2" align="left" valign="top">4th min</entry><entry namest="col3" nameend="col3" align="left" valign="top">1/2 silica, Vulkanox, protector</entry></row><row rowsep="0"><entry namest="col1" nameend="col1" align="left" valign="top" /><entry namest="col2" nameend="col2" align="left" valign="top">4th min</entry><entry namest="col3" nameend="col3" align="left" valign="top">Clean</entry></row><row rowsep="0"><entry namest="col1" nameend="col1" align="left" valign="top">4th to</entry><entry namest="col2" nameend="col2" align="left" valign="top">5 min</entry><entry namest="col3" nameend="col3" align="left" valign="top">Mix</entry></row><row rowsep="0"><entry namest="col1" nameend="col1" align="left" valign="top" /><entry namest="col2" nameend="col2" align="left" valign="top">5 min</entry><entry namest="col3" nameend="col3" align="left" valign="top">Airing</entry></row><row rowsep="0"><entry namest="col1" nameend="col1" align="left" valign="top">5 to</entry><entry namest="col2" nameend="col2" align="left" valign="top">6 min</entry><entry namest="col3" nameend="col3" align="left" valign="top">Mix and extend</entry></row><row><entry namest="col1" nameend="col2" colsep="1" rowsep="0" align="left" valign="top" /><entry namest="col3" nameend="col3" rowsep="0" align="left" valign="top" /></row><row rowsep="0"><entry namest="col1" nameend="col2" colsep="1" rowsep="0" align="left" valign="top">Batch temp.</entry><entry namest="col3" nameend="col3" align="left" valign="top">145-155 ° C</entry></row><row><entry namest="col1" nameend="col2" colsep="1" rowsep="1" align="left" valign="top">storage</entry><entry namest="col3" nameend="col3" align="left" valign="top">24th h at room temperature</entry></row><row><entry namest="col1" nameend="col3" colsep="1" rowsep="1" align="left" valign="top" /></row></tbody></tgroup><tgroup cols="3" colsep="1" rowsep="1"><colspec colnum="1" colname="col1" colwidth="16mm" colsep="0" /><colspec colnum="2" colname="col2" colwidth="16mm" colsep="1" /><colspec colnum="3" colname="col3" colwidth="134mm" colsep="1" /><thead><row><entry namest="col1" nameend="col3" colsep="1" rowsep="1" align="center" valign="top">Level 2</entry></row><row><entry namest="col1" nameend="col2" colsep="1" rowsep="1" align="left" valign="top">Settings</entry><entry namest="col3" nameend="col3" align="left" valign="top" /></row></thead><tbody><row rowsep="0"><entry namest="col1" nameend="col2" colsep="1" rowsep="0" align="left" valign="top">Mixing unit</entry><entry namest="col3" nameend="col3" align="left" valign="top">As in level 1 except:</entry></row><row rowsep="0"><entry namest="col1" nameend="col2" colsep="1" rowsep="0" align="left" valign="top">rotational speed</entry><entry namest="col3" nameend="col3" align="left" valign="top">70 min<sup>-1</sup></entry></row><row rowsep="0"><entry namest="col1" nameend="col2" colsep="1" rowsep="0" align="left" valign="top">Flow temp.</entry><entry namest="col3" nameend="col3" align="left" valign="top">80 ° C</entry></row><row><entry namest="col1" nameend="col2" colsep="1" rowsep="1" align="left" valign="top">Degree of filling</entry><entry namest="col3" nameend="col3" align="left" valign="top">0,54</entry></row></tbody></tgroup><tgroup cols="3" colsep="1" rowsep="1"><colspec colnum="1" colname="col1" colwidth="16mm" colsep="0" /><colspec colnum="2" colname="col2" colwidth="16mm" colsep="1" /><colspec colnum="3" colname="col3" colwidth="134mm" colsep="1" /><thead><row><entry namest="col1" nameend="col2" colsep="1" rowsep="1" align="left" valign="top">Mixing process</entry><entry namest="col3" nameend="col3" align="left" valign="top" /></row></thead><tbody><row rowsep="0"><entry namest="col1" nameend="col1" align="left" valign="top">0 to</entry><entry namest="col2" nameend="col2" align="left" valign="top">2nd min</entry><entry namest="col3" nameend="col3" align="left" valign="top">Batch break level 1</entry></row><row rowsep="0"><entry namest="col1" nameend="col1" align="left" valign="top">2nd to</entry><entry namest="col2" nameend="col2" align="left" valign="top">5 min</entry><entry namest="col3" nameend="col3" align="left" valign="top">Keep the batch temperature at 150 ° C by varying the speed</entry></row><row rowsep="0"><entry namest="col1" nameend="col1" align="left" valign="top" /><entry namest="col2" nameend="col2" align="left" valign="top">5 min</entry><entry namest="col3" nameend="col3" align="left" valign="top">Extend</entry></row><row><entry namest="col1" nameend="col2" rowsep="0" align="left" valign="top" /><entry namest="col3" nameend="col3" rowsep="0" align="left" valign="top" /></row><row rowsep="0"><entry namest="col1" nameend="col2" colsep="1" rowsep="0" align="left" valign="top">Batch temp.</entry><entry namest="col3" nameend="col3" align="left" valign="top">145-155 ° C</entry></row><row><entry namest="col1" nameend="col2" colsep="1" rowsep="1" align="left" valign="top">storage</entry><entry namest="col3" nameend="col3" align="left" valign="top">4th h at room temperature</entry></row></tbody></tgroup><tgroup cols="3" colsep="1" rowsep="1"><colspec colnum="1" colname="col1" colwidth="16mm" colsep="0" /><colspec colnum="2" colname="col2" colwidth="16mm" colsep="1" /><colspec colnum="3" colname="col3" colwidth="134mm" colsep="1" /><thead><row><entry namest="col1" nameend="col3" colsep="1" rowsep="1" align="center" valign="top">level 3</entry></row><row><entry namest="col1" nameend="col2" colsep="1" rowsep="1" align="left" valign="top">Settings</entry><entry namest="col3" nameend="col3" align="left" valign="top" /></row></thead><tbody><row rowsep="0"><entry namest="col1" nameend="col2" colsep="1" rowsep="0" align="left" valign="top">Mixing unit</entry><entry namest="col3" nameend="col3" align="left" valign="top">as in level 1 to</entry></row><row rowsep="0"><entry namest="col1" nameend="col2" colsep="1" rowsep="0" align="left" valign="top">rotational speed</entry><entry namest="col3" nameend="col3" align="left" valign="top">40 min<sup>-1</sup></entry></row><row rowsep="0"><entry namest="col1" nameend="col2" colsep="1" rowsep="0" align="left" valign="top">Degree of filling</entry><entry namest="col3" nameend="col3" align="left" valign="top">0,52</entry></row><row><entry namest="col1" nameend="col2" colsep="1" rowsep="1" align="left" valign="top">Flow temp.</entry><entry namest="col3" nameend="col3" align="left" valign="top">50 ° C</entry></row></tbody></tgroup><tgroup cols="3" colsep="1" rowsep="1"><colspec colnum="1" colname="col1" colwidth="16mm" colsep="0" /><colspec colnum="2" colname="col2" colwidth="16mm" colsep="1" /><colspec colnum="3" colname="col3" colwidth="134mm" colsep="1" /><thead><row><entry namest="col1" nameend="col2" colsep="1" rowsep="1" align="left" valign="top">Mixing process</entry><entry namest="col3" nameend="col3" align="left" valign="top" /></row></thead><tbody><row rowsep="0"><entry namest="col1" nameend="col1" align="left" valign="top">0 to</entry><entry namest="col2" nameend="col2" align="left" valign="top">2nd min</entry><entry namest="col3" nameend="col3" align="left" valign="top">Batch level 2, accelerator, sulfur</entry></row><row rowsep="0"><entry namest="col1" nameend="col1" align="left" valign="top" /><entry namest="col2" nameend="col2" align="left" valign="top">2nd min</entry><entry namest="col3" nameend="col3" align="left" valign="top">extend and form fur on laboratory mixing mill</entry></row><row rowsep="0"><entry namest="col1" nameend="col2" colsep="1" rowsep="0" align="left" valign="top" /><entry namest="col3" nameend="col3" align="left" valign="top">(Diameter 200 mm, length 450 mm, flow temperature 50 ° C)</entry></row><row><entry namest="col1" nameend="col2" colsep="1" rowsep="0" align="left" valign="top" /><entry namest="col3" nameend="col3" rowsep="0" align="left" valign="top" /></row><row rowsep="0"><entry namest="col1" nameend="col2" colsep="1" rowsep="0" align="left" valign="top" /><entry namest="col3" nameend="col3" align="left" valign="top">Homogenize:</entry></row><row rowsep="0"><entry namest="col1" nameend="col2" colsep="1" rowsep="0" align="left" valign="top" /><entry namest="col3" nameend="col3" align="left" valign="top">Cut 5 * left, 5 * right and pull out 6 * with a wide roller gap (6 mm) and 3 * with a narrow roller gap (3 mm).</entry></row><row><entry namest="col1" nameend="col2" colsep="1" rowsep="1" align="left" valign="top">Batch temp.</entry><entry namest="col3" nameend="col3" align="left" valign="top"><110 ° C</entry></row></tbody></tgroup></table></tables>
Table 3 lists the methods for rubber testing.<tables id="tabl0004" num="0004"><table frame="all"><title>Table 3:</title><tgroup cols="2" colsep="0" rowsep="1"><colspec colnum="1" colname="col1" colwidth="49mm" colsep="0" /><colspec colnum="2" colname="col2" colwidth="33mm" colsep="1" /><thead><row><entry namest="col1" nameend="col1" align="left" valign="top">Physical testing</entry><entry namest="col2" nameend="col2" align="left" valign="top">Norm / conditions</entry></row></thead><tbody><row rowsep="0"><entry namest="col1" nameend="col1" align="left" valign="top">Tensile test on the ring, 23 ° C</entry><entry namest="col2" nameend="col2" align="left" valign="top">DIN 53504, ISO 37</entry></row><row rowsep="0"><entry namest="col1" nameend="col1" align="left" valign="top">Tensile strength (MPa)</entry><entry namest="col2" nameend="col2" align="left" valign="top" /></row><row rowsep="0"><entry namest="col1" nameend="col1" align="left" valign="top">Stress values (MPa)</entry><entry namest="col2" nameend="col2" align="left" valign="top" /></row><row><entry namest="col1" nameend="col1" align="left" valign="top">Elongation at break (%)</entry><entry namest="col2" nameend="col2" align="left" valign="top" /></row><row><entry namest="col1" nameend="col1" align="left" valign="top">Tear attempt to Graves</entry><entry namest="col2" nameend="col2" align="left" valign="top">DIN 53 515</entry></row><row><entry namest="col1" nameend="col1" align="left" valign="top">DIN abrasion, 10 N force (mm<sup>3</sup>)</entry><entry namest="col2" nameend="col2" align="left" valign="top">DIN 53 516</entry></row><row><entry namest="col1" nameend="col1" align="left" valign="top">Ball rebound, 60 ° C (%)</entry><entry namest="col2" nameend="col2" align="left" valign="top">ASTM D 5308</entry></row></tbody></tgroup></table></tables>
Table 4 shows the results of the rubber test.<tables id="tabl0005" num="0005"><table frame="all"><title>Table 4:</title><tgroup cols="6" colsep="1" rowsep="1"><colspec colnum="1" colname="col1" colwidth="37mm" colsep="1" /><colspec colnum="2" colname="col2" colwidth="16mm" colsep="1" /><colspec colnum="3" colname="col3" colwidth="31mm" colsep="1" /><colspec colnum="4" colname="col4" colwidth="31mm" colsep="1" /><colspec colnum="5" colname="col5" colwidth="31mm" colsep="1" /><colspec colnum="6" colname="col6" colwidth="22mm" colsep="1" /><thead><row><entry namest="col1" nameend="col1" align="left" valign="top"><b>Vulcanizate data</b></entry><entry namest="col2" nameend="col2" align="left" valign="top"><b>unit</b></entry><entry namest="col3" nameend="col3" align="left" valign="top"><b>Mix 1 (Ref.)</b></entry><entry namest="col4" nameend="col4" align="left" valign="top"><b>Mix 2 (Ref.)</b></entry><entry namest="col5" nameend="col5" align="left" valign="top"><b>Mix 3 (Ref.)</b></entry><entry namest="col6" nameend="col6" align="left" valign="top"><b>Mix 4</b></entry></row></thead><tbody><row><entry namest="col1" nameend="col1" align="left" valign="top">tensile strenght</entry><entry namest="col2" nameend="col2" align="left" valign="top">[MPa]</entry><entry namest="col3" nameend="col3" align="left" valign="top">12,8</entry><entry namest="col4" nameend="col4" align="left" valign="top">15,2</entry><entry namest="col5" nameend="col5" align="left" valign="top">12,2</entry><entry namest="col6" nameend="col6" align="left" valign="top">15,2</entry></row><row><entry namest="col1" nameend="col1" align="left" valign="top">Voltage value 100%</entry><entry namest="col2" nameend="col2" align="left" valign="top">[MPa]</entry><entry namest="col3" nameend="col3" align="left" valign="top">1,2</entry><entry namest="col4" nameend="col4" align="left" valign="top">1,2</entry><entry namest="col5" nameend="col5" align="left" valign="top">1,3</entry><entry namest="col6" nameend="col6" align="left" valign="top">1,2</entry></row><row><entry namest="col1" nameend="col1" align="left" valign="top">Voltage value 300%</entry><entry namest="col2" nameend="col2" align="left" valign="top">[MPa]</entry><entry namest="col3" nameend="col3" align="left" valign="top">5,8</entry><entry namest="col4" nameend="col4" align="left" valign="top">6,2</entry><entry namest="col5" nameend="col5" align="left" valign="top">6,1</entry><entry namest="col6" nameend="col6" align="left" valign="top">6,7</entry></row><row><entry namest="col1" nameend="col1" align="left" valign="top">Voltage value 300% / 100%</entry><entry namest="col2" nameend="col2" align="left" valign="top">[-]</entry><entry namest="col3" nameend="col3" align="left" valign="top">4,8</entry><entry namest="col4" nameend="col4" align="left" valign="top">5,2</entry><entry namest="col5" nameend="col5" align="left" valign="top">4,7</entry><entry namest="col6" nameend="col6" align="left" valign="top">5,6</entry></row><row><entry namest="col1" nameend="col1" align="left" valign="top">Elongation at break</entry><entry namest="col2" nameend="col2" align="left" valign="top">[%]</entry><entry namest="col3" nameend="col3" align="left" valign="top">480</entry><entry namest="col4" nameend="col4" align="left" valign="top">480</entry><entry namest="col5" nameend="col5" align="left" valign="top">460</entry><entry namest="col6" nameend="col6" align="left" valign="top">460</entry></row><row><entry namest="col1" nameend="col1" align="left" valign="top">Tear resistance</entry><entry namest="col2" nameend="col2" align="left" valign="top">[N / mm]</entry><entry namest="col3" nameend="col3" align="left" valign="top">53</entry><entry namest="col4" nameend="col4" align="left" valign="top">63</entry><entry namest="col5" nameend="col5" align="left" valign="top">45</entry><entry namest="col6" nameend="col6" align="left" valign="top">74</entry></row><row><entry namest="col1" nameend="col1" align="left" valign="top">Ball rebound (60 ° C)</entry><entry namest="col2" nameend="col2" align="left" valign="top">[%]</entry><entry namest="col3" nameend="col3" align="left" valign="top">65,5</entry><entry namest="col4" nameend="col4" align="left" valign="top">69,5</entry><entry namest="col5" nameend="col5" align="left" valign="top">65,1</entry><entry namest="col6" nameend="col6" align="left" valign="top">69,1</entry></row><row><entry namest="col1" nameend="col1" align="left" valign="top">DIN abrasion</entry><entry namest="col2" nameend="col2" align="left" valign="top">[mm<sup>3</sup>]</entry><entry namest="col3" nameend="col3" align="left" valign="top">88</entry><entry namest="col4" nameend="col4" align="left" valign="top">66</entry><entry namest="col5" nameend="col5" align="left" valign="top">82</entry><entry namest="col6" nameend="col6" align="left" valign="top">59</entry></row></tbody></tgroup></table></tables>
It is known from DE10015309A1 that mercaptosilanes have a higher coupling yield and thus reinforcement than a polysulfide. This is confirmed by the comparison of mixture 2 to mixture 1 by the higher gain factor (tension value 300% / 100%), the higher ball rebound value and the improved (lower) DIN abrasion.
EP 1043357 A1 shows for triethoxysilylpropyl disulfide (example 1) that the substitution of two ethoxy groups per silicon atom by methyl groups (example 2) does not impair the rubber properties, such as static data such as tensile strength and tension values, and dynamic data , such as ball rebound, dynamic moduli and tan δ, compared to the triethoxy variant.
In contrast to the aforementioned observations for the polysulfides from EP 1043357, the dimethyl variant of the mercaptosilane (mixture 4 according to the invention) shows significant improvements in important properties. The tension value at 300% elongation, the reinforcement factor (tension value 300% / 100%), the tear propagation resistance and the DIN abrasion are significantly better than with the corresponding triethoxy variant (MPTES) (mixture 2). They are also significantly better than TESPT (mixture 1) and the corresponding dimethyl variant DMESPT (mixture 3).
Example 3: HS-CH
2
-CH
2
-CH
2
-Si (Me) (OMe) [(0-CH (CH
3
) -CH
2
)
5-
0-C
4
H
9
]
86.64 g of HS-CH<sub>2</sub>-CH<sub>2</sub>-CH<sub>2-</sub>Si (Me) (OMe)<sub>2</sub> , 163.29 g polypropylene glycol monobutyl ether (CAS 9003-13-8, company Aldrich, M<sub>w</sub> = 340 g / mol) and 0.23 g of p-toluenesulfonic acid mixed. The mixture is treated on a rotary evaporator at an oil bath temperature of 150-155 ° C. and 100-400 mbar for 6.5 h. The volatile alcohol released is distilled off. The isolated weight of the product is 236 g.
Example 4: HS-CH
2
-CH
2
-CH
2
-Si (Me) (OMe) [(O-CH (CH
3
) -CH
2
)
16-
OC
4
H
9
]
86.64 g of HS-CH<sub>2</sub>-CH<sub>2</sub>-CH<sub>2-</sub>Si (Me) (OMe)<sub>2</sub> , 480.03 g polypropylene glycol monobutyl ether (CAS 9003-13-8, company Aldrich, M<sub>w</sub> = 1000 g / mol) and 0.23 g of p-toluenesulfonic acid mixed. The mixture is treated on a rotary evaporator at an oil bath temperature of 145-155 ° C. and 100-400 mbar for 4.5 h. The volatile alcohol released is distilled off. The isolated weight of the product is 552 g.
Example 5: HS-CH
2
-CH
2
-CH
2
-Si (Me) (OMe) [(O-CH
2
-CH
2
)
4
-O-CH
2
-CH (Et) -C
4
H
9
]
86.62 g of HS-CH<sub>2</sub>-CH<sub>2</sub>-CH<sub>2-</sub>Si (Me) (OMe)<sub>2</sub> , 147 g polyethylene glycol mono-2-ethylhexyl ether (Aduxol HEX-04, CAS 26468-86-0, company Schärer & Schläpfer AG) and 0.5 g Ti (OBu)<sub>4</sub> mixed. The mixture is treated on a rotary evaporator at an oil bath temperature of 125-135 ° C. and 150-300 mbar for 4.5 h. The volatile alcohol released is distilled off. The isolated weight of the product is 214 g.
Example 6: HS-CH
2
-CH
2
-CH
2
-Si (Me) (OEt) [(O-CH
2
-CH
2
)
2
-OC
6
H
13
]
50 g of HS-CH<sub>2</sub>-CH<sub>2</sub>-CH<sub>2-</sub>Si (Me) (OEt)<sub>2</sub>, 45.7 g diethylene glycol monohexyl ether (CAS 112-59-4, obtained from Merck / VWR International) and 0.23 g Ti (OBu)<sub>4</sub> mixed. The mixture is treated on a rotary evaporator at an oil bath temperature of 130-135 ° C and 100-300 mbar for 6 h. The volatile alcohol released is distilled off. The amount of isolated product is 80 g.
Example 7: HS-CH
2
-CH
2
-CH
2
-Si (Me) (OEt) [(O-CH (CH
3
) -CH
2
)
16-
OC
4
H
9
]
80 g of HS-CH<sub>2</sub>-CH<sub>2</sub>-CH<sub>2-</sub>Si (Me) (OEt)<sub>2</sub>, 384.07 g polypropylene glycol monobutyl ether (CAS 9003-13-8, company Aldrich, M<sub>w</sub> = 1000 g / mol) and 0.2 g of p-toluenesulfonic acid mixed. The mixture is treated on a rotary evaporator at an oil bath temperature of 145-155 ° C. and 100-300 mbar for 6 h. The volatile alcohol released is distilled off. The weight of the product obtained is 448 g.
Example 8: HS-CH
2
-CH
2
-CH
2
-Si (Me) (OEt) [(O-CH
2
-CH
2
)
4
-O-CH
2
-CH (Et) -C
4
H
9
]
50 g of HS-CH<sub>2</sub>-CH<sub>2</sub>-CH<sub>2-</sub>Si (Me) (OEt)<sub>2</sub>, 73.5 g of polyethylene glycol mono-2-ethylhexyl ether (Aduxol HEX-04, CAS 26468-86-0, from Schärer & Schläpfer AG) and 0.3 g of Ti (OBu)<sub>4</sub> mixed. The mixture is treated on a rotary evaporator at an oil bath temperature of 125-135 ° C. and 150-300 mbar for 4.5 h. The volatile alcohol released is distilled off. The weight of product obtained is 108 g.
Example 9: Preparation of HS-CH
2
-CH
2
-CH
2
-SiMe (OEt)
2
HS-CH<sub>2</sub>-CH<sub>2</sub>-CH<sub>2</sub>-SiMe (OEt)<sub>2</sub> is produced based on EP 1 538 152 A1 example 4. Cl-CH<sub>2</sub>-CH<sub>2</sub>-CH<sub>2</sub>-SiMe (OEt)<sub>2</sub>, Cl-CH<sub>2</sub>-CH<sub>2</sub>-CH<sub>2</sub>-SiMeCl<sub>2</sub>, NaSH (dried) and ethanol are used. The suspension obtained is filtered, the solvent is removed and the silane is purified by distillation.
Example 10: Rubber engineering studies
The formulation used for the rubber compounds is shown in Table 5 below. The mixtures differ in the coupling agent added, as indicated in Table 6. The mixing instructions are listed in Table 2.<tables id="tabl0006" num="0006"><table frame="all"><title>Table 5:</title><tgroup cols="2" colsep="0" rowsep="1"><colspec colnum="1" colname="col1" colwidth="32mm" colsep="0" /><colspec colnum="2" colname="col2" colwidth="40mm" colsep="1" /><thead><row><entry namest="col1" nameend="col1" align="left" valign="top">substance</entry><entry namest="col2" nameend="col2" align="left" valign="top">Mixtures 5 to 13 [phr]</entry></row><row><entry namest="col1" nameend="col2" colsep="1" rowsep="1" align="left" valign="top"><b>1. step</b></entry></row></thead><tbody><row rowsep="0"><entry namest="col1" nameend="col1" align="left" valign="top">Buna VSL 5025-1</entry><entry namest="col2" nameend="col2" align="left" valign="top">96</entry></row><row rowsep="0"><entry namest="col1" nameend="col1" align="left" valign="top">Buna CB 24</entry><entry namest="col2" nameend="col2" align="left" valign="top">30</entry></row><row rowsep="0"><entry namest="col1" nameend="col1" align="left" valign="top">Ultrasil 7000 GR</entry><entry namest="col2" nameend="col2" align="left" valign="top">80</entry></row><row rowsep="0"><entry namest="col1" nameend="col1" align="left" valign="top">Silanes from Table 6</entry><entry namest="col2" nameend="col2" align="left" valign="top">2</entry></row><row rowsep="0"><entry namest="col1" nameend="col1" align="left" valign="top">ZnO</entry><entry namest="col2" nameend="col2" align="left" valign="top">3</entry></row><row rowsep="0"><entry namest="col1" nameend="col1" align="left" valign="top">Stearic acid</entry><entry namest="col2" nameend="col2" align="left" valign="top">2</entry></row><row rowsep="0"><entry namest="col1" nameend="col1" align="left" valign="top">Naftolen ZD</entry><entry namest="col2" nameend="col2" align="left" valign="top">10</entry></row><row rowsep="0"><entry namest="col1" nameend="col1" align="left" valign="top">Vulkanox 4020</entry><entry namest="col2" nameend="col2" align="left" valign="top">1,5</entry></row><row><entry namest="col1" nameend="col1" align="left" valign="top">Protector G 3108</entry><entry namest="col2" nameend="col2" align="left" valign="top">1</entry></row></tbody></tgroup><tgroup cols="2" colsep="0" rowsep="1"><colspec colnum="1" colname="col1" colwidth="32mm" colsep="0" /><colspec colnum="2" colname="col2" colwidth="40mm" colsep="1" /><thead><row><entry namest="col1" nameend="col2" colsep="1" rowsep="1" align="left" valign="top"><b>2nd step</b></entry></row></thead><tbody><row><entry namest="col1" nameend="col1" align="left" valign="top">Batch level 1</entry><entry namest="col2" nameend="col2" align="left" valign="top" /></row></tbody></tgroup><tgroup cols="2" colsep="0" rowsep="1"><colspec colnum="1" colname="col1" colwidth="32mm" colsep="0" /><colspec colnum="2" colname="col2" colwidth="40mm" colsep="1" /><thead><row><entry namest="col1" nameend="col2" colsep="1" rowsep="1" align="left" valign="top"><b>3rd step</b></entry></row></thead><tbody><row rowsep="0"><entry namest="col1" nameend="col1" align="left" valign="top">Batch level 2</entry><entry namest="col2" nameend="col2" align="left" valign="top" /></row><row rowsep="0"><entry namest="col1" nameend="col1" align="left" valign="top">Vulkacit D</entry><entry namest="col2" nameend="col2" align="left" valign="top">2</entry></row><row rowsep="0"><entry namest="col1" nameend="col1" align="left" valign="top">Vulkacit CZ</entry><entry namest="col2" nameend="col2" align="left" valign="top">1,5</entry></row><row><entry namest="col1" nameend="col1" align="left" valign="top">Perkacit TBzTD</entry><entry namest="col2" nameend="col2" align="left" valign="top">0,2</entry></row><row><entry namest="col1" nameend="col1" align="left" valign="top">sulfur</entry><entry namest="col2" nameend="col2" align="left" valign="top">1,5</entry></row></tbody></tgroup></table></tables><tables id="tabl0007" num="0007"><table frame="all"><title>Table 6:</title><tgroup cols="2" colsep="1" rowsep="1"><colspec colnum="1" colname="col1" colwidth="24mm" colsep="1" /><colspec colnum="2" colname="col2" colwidth="32mm" colsep="1" /><thead><row><entry namest="col1" nameend="col1" align="left" valign="top">Mix number</entry><entry namest="col2" nameend="col2" align="left" valign="top">Silane</entry></row></thead><tbody><row><entry namest="col1" nameend="col1" align="left" valign="top">5 (Ref.)</entry><entry namest="col2" nameend="col2" align="left" valign="top">VP Si 263</entry></row><row><entry namest="col1" nameend="col1" align="left" valign="top">6</entry><entry namest="col2" nameend="col2" align="left" valign="top">Silane from Example 1</entry></row><row><entry namest="col1" nameend="col1" align="left" valign="top">7</entry><entry namest="col2" nameend="col2" align="left" valign="top">Silane from Example 9</entry></row><row><entry namest="col1" nameend="col1" align="left" valign="top">8</entry><entry namest="col2" nameend="col2" align="left" valign="top">Silane from Example 3</entry></row><row><entry namest="col1" nameend="col1" align="left" valign="top">9</entry><entry namest="col2" nameend="col2" align="left" valign="top">Silane from Example 4</entry></row><row><entry namest="col1" nameend="col1" align="left" valign="top">10</entry><entry namest="col2" nameend="col2" align="left" valign="top">Silane from Example 5</entry></row><row><entry namest="col1" nameend="col1" align="left" valign="top">11</entry><entry namest="col2" nameend="col2" align="left" valign="top">Silane from example 6</entry></row><row><entry namest="col1" nameend="col1" align="left" valign="top">12</entry><entry namest="col2" nameend="col2" align="left" valign="top">Silane from Example 7</entry></row><row><entry namest="col1" nameend="col1" align="left" valign="top">13</entry><entry namest="col2" nameend="col2" align="left" valign="top">Silane from Example 8</entry></row></tbody></tgroup></table></tables>
Table 7 lists the methods for rubber testing.<tables id="tabl0008" num="0008"><table frame="all"><title>Table 7:</title><tgroup cols="2" colsep="0" rowsep="1"><colspec colnum="1" colname="col1" colwidth="52mm" colsep="0" /><colspec colnum="2" colname="col2" colwidth="35mm" colsep="1" /><thead><row><entry namest="col1" nameend="col1" align="left" valign="top">Physical testing</entry><entry namest="col2" nameend="col2" align="left" valign="top">Norm / conditions</entry></row></thead><tbody><row rowsep="0"><entry namest="col1" nameend="col1" align="left" valign="top">Scorching behavior, 130 ° C</entry><entry namest="col2" nameend="col2" align="left" valign="top">DIN 53523/4, ISO 667</entry></row><row rowsep="0"><entry namest="col1" nameend="col1" align="left" valign="top">Scorch time t<sub>5</sub></entry><entry namest="col2" nameend="col2" align="left" valign="top" /></row><row><entry namest="col1" nameend="col1" align="left" valign="top">Scorch time t<sub>35</sub></entry><entry namest="col2" nameend="col2" align="left" valign="top" /></row><row><entry namest="col1" nameend="col1" align="left" valign="top">Tear test DIE A</entry><entry namest="col2" nameend="col2" align="left" valign="top">ASTM D 624</entry></row><row><entry namest="col1" nameend="col1" align="left" valign="top">Tear test DIE B</entry><entry namest="col2" nameend="col2" align="left" valign="top">ASTM D 624</entry></row></tbody></tgroup></table></tables>
Table 8 shows the results of the rubber test.<tables id="tabl0009" num="0009"><img file="EP1672017A2_D0001.tif" /></tables>
As can be seen from the vulcanizate results, the tear resistance of mixtures 8 to 13 is significantly better than that of mixtures 5, 6, 7. The mixtures with the silanes with long-chain alcohol as substituents show improved tear propagation behavior compared to the other mixtures. This applies both to unsubstituted mercaptosilane from mixture 5 (VP Si 263) and to mercaptosilanes with one methyl group (mixture 7) and with two methyl groups (mixture 6).
Mixtures 8 to 13 also show improved Mooney-Scorch data. This is associated with improved processing reliability, for example in the extrusion of tire treads or injection molding.
Example 11: Rubber-technical investigations
The formulation used for the rubber compounds is given in Table 9 below. The mixtures differ in the coupling agent added based on equimolar dosing as indicated in Table 10. The mixing instructions are listed in Table 2.<tables id="tabl0010" num="0010"><table frame="all"><title>Table 9:</title><tgroup cols="2" colsep="0" rowsep="1"><colspec colnum="1" colname="col1" colwidth="34mm" colsep="0" /><colspec colnum="2" colname="col2" colwidth="42mm" colsep="1" /><thead><row><entry namest="col1" nameend="col1" align="left" valign="top">substance</entry><entry namest="col2" nameend="col2" align="left" valign="top">Mixtures 14 to 21 [phr]</entry></row><row><entry namest="col1" nameend="col2" colsep="1" rowsep="1" align="left" valign="top"><b>1. step</b></entry></row></thead><tbody><row rowsep="0"><entry namest="col1" nameend="col1" align="left" valign="top">Buna VSL 5025-1</entry><entry namest="col2" nameend="col2" align="left" valign="top">96</entry></row><row rowsep="0"><entry namest="col1" nameend="col1" align="left" valign="top">Buna CB 24</entry><entry namest="col2" nameend="col2" align="left" valign="top">30</entry></row><row rowsep="0"><entry namest="col1" nameend="col1" align="left" valign="top">Ultrasil 7000 GR</entry><entry namest="col2" nameend="col2" align="left" valign="top">80</entry></row><row rowsep="0"><entry namest="col1" nameend="col1" align="left" valign="top">Silanes from Table 10</entry><entry namest="col2" nameend="col2" align="left" valign="top">equimolar</entry></row><row rowsep="0"><entry namest="col1" nameend="col1" align="left" valign="top">ZnO</entry><entry namest="col2" nameend="col2" align="left" valign="top">3</entry></row><row rowsep="0"><entry namest="col1" nameend="col1" align="left" valign="top">Stearic acid</entry><entry namest="col2" nameend="col2" align="left" valign="top">2</entry></row><row rowsep="0"><entry namest="col1" nameend="col1" align="left" valign="top">Naftolen ZD</entry><entry namest="col2" nameend="col2" align="left" valign="top">10</entry></row><row rowsep="0"><entry namest="col1" nameend="col1" align="left" valign="top">Vulkanox 4020</entry><entry namest="col2" nameend="col2" align="left" valign="top">1,5</entry></row><row><entry namest="col1" nameend="col1" align="left" valign="top">Protector G 3108</entry><entry namest="col2" nameend="col2" align="left" valign="top">1</entry></row></tbody></tgroup><tgroup cols="2" colsep="0" rowsep="1"><colspec colnum="1" colname="col1" colwidth="34mm" colsep="0" /><colspec colnum="2" colname="col2" colwidth="42mm" colsep="1" /><thead><row><entry namest="col1" nameend="col2" colsep="1" rowsep="1" align="left" valign="top"><b>2nd step</b></entry></row></thead><tbody><row><entry namest="col1" nameend="col1" align="left" valign="top">Batch level 1</entry><entry namest="col2" nameend="col2" align="left" valign="top" /></row></tbody></tgroup><tgroup cols="2" colsep="0" rowsep="1"><colspec colnum="1" colname="col1" colwidth="34mm" colsep="0" /><colspec colnum="2" colname="col2" colwidth="42mm" colsep="1" /><thead><row><entry namest="col1" nameend="col2" colsep="1" rowsep="1" align="left" valign="top"><b>3rd step</b></entry></row></thead><tbody><row rowsep="0"><entry namest="col1" nameend="col1" align="left" valign="top">Batch level 2</entry><entry namest="col2" nameend="col2" align="left" valign="top" /></row><row rowsep="0"><entry namest="col1" nameend="col1" align="left" valign="top">Vulkacit D</entry><entry namest="col2" nameend="col2" align="left" valign="top">2</entry></row><row rowsep="0"><entry namest="col1" nameend="col1" align="left" valign="top">Vulkacit CZ</entry><entry namest="col2" nameend="col2" align="left" valign="top">1,5</entry></row><row><entry namest="col1" nameend="col1" align="left" valign="top">Perkacit TBzTD</entry><entry namest="col2" nameend="col2" align="left" valign="top">0,2</entry></row><row><entry namest="col1" nameend="col1" align="left" valign="top">sulfur</entry><entry namest="col2" nameend="col2" align="left" valign="top">1,5</entry></row></tbody></tgroup></table></tables><tables id="tabl0011" num="0011"><table frame="all"><title>Table 10:</title><tgroup cols="3" colsep="1" rowsep="1"><colspec colnum="1" colname="col1" colwidth="24mm" colsep="1" /><colspec colnum="2" colname="col2" colwidth="32mm" colsep="1" /><colspec colnum="3" colname="col3" colwidth="12mm" colsep="1" /><thead><row><entry namest="col1" nameend="col1" align="left" valign="top">Mix number</entry><entry namest="col2" nameend="col2" align="left" valign="top">Silane</entry><entry namest="col3" nameend="col3" align="left" valign="top">phr</entry></row></thead><tbody><row><entry namest="col1" nameend="col1" align="left" valign="top">14</entry><entry namest="col2" nameend="col2" align="left" valign="top">VP Si 263</entry><entry namest="col3" nameend="col3" valign="top" align="char" char="." charoff="59">2,00</entry></row><row><entry namest="col1" nameend="col1" align="left" valign="top">15</entry><entry namest="col2" nameend="col2" align="left" valign="top">Silane from Example 9</entry><entry namest="col3" nameend="col3" valign="top" align="char" char="." charoff="59">1,75</entry></row><row><entry namest="col1" nameend="col1" align="left" valign="top">16</entry><entry namest="col2" nameend="col2" align="left" valign="top">Silane from Example 3</entry><entry namest="col3" nameend="col3" valign="top" align="char" char="." charoff="59">4,31</entry></row><row><entry namest="col1" nameend="col1" align="left" valign="top">17</entry><entry namest="col2" nameend="col2" align="left" valign="top">Silane from Example 4</entry><entry namest="col3" nameend="col3" valign="top" align="char" char="." charoff="59">9,68</entry></row><row><entry namest="col1" nameend="col1" align="left" valign="top">18</entry><entry namest="col2" nameend="col2" align="left" valign="top">Silane from Example 5</entry><entry namest="col3" nameend="col3" valign="top" align="char" char="." charoff="59">3,82</entry></row><row><entry namest="col1" nameend="col1" align="left" valign="top">19</entry><entry namest="col2" nameend="col2" align="left" valign="top">Silane from example 6</entry><entry namest="col3" nameend="col3" valign="top" align="char" char="." charoff="59">2,97</entry></row><row><entry namest="col1" nameend="col1" align="left" valign="top">20</entry><entry namest="col2" nameend="col2" align="left" valign="top">Silane from Example 7</entry><entry namest="col3" nameend="col3" valign="top" align="char" char="." charoff="59">9,80</entry></row><row><entry namest="col1" nameend="col1" align="left" valign="top">21</entry><entry namest="col2" nameend="col2" align="left" valign="top">Silane from Example 8</entry><entry namest="col3" nameend="col3" valign="top" align="char" char="." charoff="59">3,94</entry></row></tbody></tgroup></table></tables>
The tests carried out are listed in Table 7. Table 11 shows the results of the rubber test.<tables id="tabl0012" num="0012"><img file="EP1672017A2_D0002.tif" /></tables>
Even with equimolar dosing, the mixtures with the silanes from Examples 3 to 8 show advantages both in tear propagation behavior and in scorch behavior compared to unsubstituted mercaptosilane and mercaptosilane with one methyl and two ethoxy groups.
Contents36
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Numbers
- Publication
- 1672017
- Publication, DOCDB
- 1672017
- Publication, EPODOC
- EP1672017
- Application
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- Application, DOCDB
- 05112090
- Application, EPODOC
- EP20050112090
Titles3
- German
- Kautschukmischungen
- English
- Rubber compositions
- French
- Mélanges de caoutchouc
Classification
- CPC, 7
- C08K5/5419
- C07F7/18
- C08K3/36
- C08K5/548
- C08L9/00
- C08L9/06
- C08L21/00
- IPC, 7
- C08L21 00
- C08K5 54
- C08L7 00
- C08K5 34
- C08K5 37
- C08L9 02
- C08L9 06
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and 7 moreShow fewer
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- Extension states, 5
- Albania
- Bosnia and Herzegovina
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- Yugoslavia, later Serbia and Montenegro (until 2006)