CROSS-LINKABLE MASSES BASED ON ORGANOSILICON COMPOUNDS

Abstract

Crosslinkable compositions, processes for producing the same and products made therefrom. Where the crosslinkable compositions include a component (A) organosilicon compounds having at least two silanol groups and having a viscosity of 10.sup.3 to 10.sup.6 mPas at 25° C., mixtures (M) containing a component (B) of organosilicon compounds of the formula (I) and/or partial hydrolyzates thereof

R.sup.6R.sup.7N—CR.sup.1.sub.2SiR.sub.a(OR.sup.2).sub.3-a  (I),

a component (C), selected from (C2) compounds of the formula (III)

R.sup.5OH  (III).

The crosslinkable compositions may optionally also include a catalyst (D).

Claims

1-9. (canceled)

10. Compositions crosslinkable by condensation reaction, comprising: wherein the compositions are producible using a component (A) organosilicon compounds having at least two silanol groups and having a viscosity of 10.sup.3 to 10.sup.6 mPas at 25° C.; mixtures (M) containing a component (B) of organosilicon compounds of the formula (I) and/or partial hydrolyzates thereof
R.sup.6R.sup.7N—CR.sup.1.sub.2SiR.sub.a(OR.sup.2).sub.3-a  (I), wherein R denotes identical or different monovalent hydrocarbon radicals; wherein R.sup.1 denotes identical or different monovalent hydrocarbon radicals or a hydrogen atom; wherein R.sup.2 may be identical or different and denotes monovalent, optionally substituted hydrocarbon radicals; wherein R.sup.6 may be identical or different and denotes monovalent, optionally substituted hydrocarbon radicals or a hydrogen atom; wherein R.sup.7 may be identical or different and denotes monovalent, optionally substituted hydrocarbon radicals, where R.sup.6 and R.sup.7 can also form a ring which may optionally be interrupted by heteroatoms; wherein a is equal to 0 or 1; a component (C), selected from (C2) compounds of the formula (III)
R.sup.5OH  (III), wherein R.sup.5 may be identical or different and denotes monovalent, optionally substituted hydrocarbon radicals; and optionally a catalyst (D).

11. The compositions of claim 10, wherein the radicals R.sup.2, R.sup.4 and R.sup.5 in the mixture (M) used have the same definition.

12. The compositions of claim 10, wherein the mixtures (M) contain the component (C) in amounts of 0.01 to 20 parts by weight, based on 100 parts by weight of component (B).

13. The compositions of claim 10, wherein the compounds (B) are N-cyclohexylaminomethyltriethoxysilane, N-phenylaminomethyltriethoxysilane, N,N-di-n-butylaminomethyltriethoxysilane, 4-(triethoxysilylmethyl)tetrahydro-1,4-oxazine or 4-(trimethoxysilylmethyl)tetrahydro-1,4-oxazine.

14. The compositions of claim 10, wherein the compositions are those producible using the (A) organosilicon compounds, the mixtures (M) containing the organosilicon compounds (B), the component (C) selected from compounds (C2), optionally a catalyst (D), optionally crosslinking catalysts (E), optionally fillers (F), optionally adhesion promoters (G), optionally plasticizers (H), optionally crosslinkers (J), and optionally additives (K).

15. A process for producing organyloxy group-comprising organosilicon compounds, comprising: providing a component (A) of organosilicon compounds having at least two silanol groups and having a viscosity of 10.sup.3 to 10.sup.6 mPas at 25° C., mixtures (M) containing a component (B) of organosilicon compounds of a formula (I) and/or the partial hydrolyzates thereof, a component (C) selected from compounds (C2) of a formula (III), and optionally a catalyst (D), wherein the formula (I) is
R.sup.6R.sup.7N—CR.sup.1.sub.2SiR.sub.a(OR.sup.2).sub.3-a  (I), wherein R denotes identical or different monovalent hydrocarbon radicals, wherein R.sup.1 denotes identical or different monovalent hydrocarbon radicals or a hydrogen atom, wherein R.sup.2 may be identical or different and denotes monovalent, optionally substituted hydrocarbon radicals, wherein R.sup.6 may be identical or different and denotes monovalent, optionally substituted hydrocarbon radicals or a hydrogen atom, wherein R.sup.7 may be identical or different and denotes monovalent, optionally substituted hydrocarbon radicals, where R.sup.6 and R.sup.7 can also form a ring which may optionally be interrupted by heteroatoms, wherein a is equal to 0 or 1, and wherein the formula (III) is
R.sup.5OH  (III), wherein R.sup.5 may be identical or different and denotes monovalent, optionally substituted hydrocarbon radicals; and mixing the components with one another and allowing them to react.

16. The process of claim 15, wherein in a first step the organosilicon compounds of component (A) are optionally in a mixture with a plasticizer (H) and the mixtures (M) are mixed with one another and allowed to react; and wherein in a second step composition obtained in the first step is mixed with at least one component selected from crosslinking catalysts (E), fillers (F), adhesion promoters (G), plasticizers (H), crosslinkers (J) and additives (K).

17. The process of claim 15, further comprising: crosslinking the compositions so as to produce a molding.

Description

EXAMPLE 1

[0104] A mixture of 490 g of an α,ω-dihydroxypolydimethylsiloxane having a viscosity of 80 000 mPa.Math.s (commercially available under the name “Polymer FD 80” from Wacker Chemie AG, Munich, Germany) and 94 g of an α,ω-bis(trimethylsiloxy)polydimethylsiloxane having a viscosity of 1000 mPa.Math.s (commercially available under the name “Weichmacher 1000” from Wacker Chemie AG, Munich, Germany) was mixed with a mixture of 16.5 g of 4-(triethoxysilylmethyl)tetrahydro-1,4-oxazine (SB1) and 0.3 g of methanol. The viscosity of the polymer mixture thus obtained was measured after 24 hours of storage at room temperature and was 67 800 mPas.

EXAMPLES 2 TO 16

[0105] The procedure described in example 1 was repeated, with the modification that the mixtures described in table 1 were used. The resulting viscosities are likewise given in table 1.

COMPARATIVE EXAMPLE 1

[0106] The procedure described in example 1 was repeated, with the modification that no methanol was used.

TABLE-US-00001 TABLE 1 Example Mixture Viscosity C1 16.8 g of — — 107 000 mPas  SB1 1 16.5 g of — 0.30 g of 67 800 mPas SB1 methanol 2 16.5 g of — 0.15 g of 78 100 mPas SB1 ethanol 3 16.5 g of — 0.30 g of 78 000 mPas SB1 ethanol 4 16.5 g of — 0.60 g of 75 000 mPas SB1 ethanol 5 16.5 g of 0.15 g of TES — 78 500 mPas SB1 6 16.5 g of 0.30 g of TES — 82 600 mPas SB1 7 16.5 g of 0.60 g of TES — 82 300 mPas SB1 8 16.5 g of 0.15 g of VTMO — 81 200 mPas SB1 9 16.5 g of 0.30 g of VTMO — 82 600 mPas SB1 10 16.5 g of 0.60 g of VTMO — 82 300 mPas SB1 11 16.5 g of 0.15 g of GF9 — 88 800 mPas SB1 12 16.5 g of 0.30 g of GF9 — 89 400 mPas SB1 13 16.5 g of 0.60 g of GF9 — 91 100 mPas SB1 14 16.5 g of 0.15 g of GF93 — 87 300 mPas SB1 15 16.5 g of 0.30 g of GF93 — 88 700 mPas SB1 16 16.5 g of 0.60 g of GF93 — 91 000 mPas SB1

EXAMPLES E18, E20 AND E21

[0107] The procedure described in example 1 was repeated, with the modification that the mixtures described in table 2 were used. The resulting viscosities are likewise given in table 2.

COMPARATIVE EXAMPLE 2

[0108] The procedure described in example 18 was repeated, with the modification that no VTMO was used.

COMPARATIVE EXAMPLE 3

[0109] The procedure described in example 20 was repeated, with the modification that no methanol was used.

TABLE-US-00002 TABLE 2 Example Mixture Viscosity C2 16.8 g of — — gelled SB2 18 16.5 g of 0.30 g of VTMO — 81 400 mPas SB2 C3 16.8 g of — — 98 300 mPas SB3 20 16.5 g of — 0.30 g 78 800 mPas SB3 of methanol 21 16.5 g of — 0.30 g 78 000 mPas SB3 of ethanol

EXAMPLE 22

[0110] A mixture of 490 g of an α,ω-dihydroxypolydimethylsiloxane having a viscosity of 80 000 mPa.Math.s (commercially available under the name “Polymer FD 80” from Wacker Chemie AG, Munich, Germany) and 94 g of an α,ω-bis(trimethylsiloxy)polydimethylsiloxane having a viscosity of 1000 mPa.Math.s (commercially available under the name “Weichmacher 1000” from Wacker Chemie AG, Munich, Germany) was mixed in a planetary mixer with a mixture of 16.5 g of 4-(triethoxysilylmethyl)tetrahydro-1,4-oxazine and 0.3 g of methanol. After stirring this mixture for 30 min, 1 g of a product J1, which was composed of 16.0 mol % of units of the formula MeSi(OEt).sub.2O.sub.1/2, 46.4 mol % of units of the formula MeSi(OEt)O.sub.2/2, 36.5 mol % of units of the formula MeSiO.sub.3/2, 0.2 mol % of units of the formula Me.sub.2Si(OEt)O.sub.1/2 and 0.9 mol % of units of the formula Me.sub.2SiO.sub.2/2, 8 g of 3-aminopropyltriethoxysilane (commercially available under the name GENIOSIL® GF 93 from Wacker Chemie AG, Munich, Germany), 2 g of vinyltriethoxysilane (commercially available under the name GENIOSIL® GF 56 from Wacker Chemie AG, Munich, Germany) and 5 g of tetraethyl silicate (commercially available under the name “Silikat TES 28” from Wacker Chemie AG, Munich, Germany) were added and the mixture was mixed for a period of 5 minutes. 45 g of a fumed silica having a BET specific surface area of 150 m.sup.2/g (commercially available under the name HDK® V15 from Wacker Chemie AG, Munich, Germany) were then mixed in and the mixture was completely homogenized at a pressure of 50 hPa. Lastly, 1 g of a 1:1 solution of octylphosphonic acid in methyltrimethoxysilane and 2 g of a reaction product of dibutyltin diacetate and tetraethoxysilane (commercially available under the name “Katalysator 41” from Wacker Chemie AG, Munich, Germany) were added and the mixture was homogenized for a further 5 min at a pressure of approx. 50 hPa (absolute).

[0111] The RTV1 composition thus obtained was filled into commercially available moisture-tight polyethylene cartridges.

[0112] Product J1 was produced by hydrolysis and condensation of methyltriethoxysilane. At 25° C. it had a density of 1.09 g/cm.sup.3 and a viscosity of 28.4 mPa.Math.s.

[0113] 2 mm-thick sheets of the sealing compound produced in example 22 were in each case spread onto a polyethylene film, and after a day of curing were detached from the film and suspended such that air could be admitted from all sides for a further 6 days, such that the samples were cured over a total of 7 days. The relative humidity was set here at 50%, with the temperature being controlled at 23° C. Test specimens of the form S2 according to DIN 53504-85 were then stamped out of these sheets and the modulus of each was determined.

[0114] To determine the hardness, 6 mm-thick specimens were produced, which were cured on PE films over 7 days at a relative humidity of 50% and at a temperature of 23° C. by reaction with the ambient atmospheric humidity.

[0115] The hardness of the sealing compound cured tack-free was 22 Shore A. The modulus (tensile stress value at 100% elongation) was determined to be 0.38 MPa. The sealing compound is thus of exceptional suitability for the sealing of building joints, for example.