Hydrolyzable and polymerizable silanes

Details Hydrolyzable and polymerizable silanes Hydrolyzable and polymerizable silanes

2001-12-13

2004-09-21

Davis, Brian (Department: 1621)

Organic compounds -- part of the class 532-570 series

Organic compounds

Silicon containing

Reexamination Certificate

active

06794527

ABSTRACT:

The invention relates to hydrolyzable and polymerizable silanes, a process for their preparation and their use for the preparation of silica polycondensates or silica heteropolycondensates and for the preparation of polymers or heteropolymers.
Hydrolyzable, organically modified silanes are widely used in the production of scratch-resistant coatings for a very wide range of substrates, and for the production of fillers, of adhesives and sealing compounds of moldings. These silanes are condensed hydrolytically either alone, as mixtures or in the presence of further hydrolyzable and/or condensable components, the final curing being effected thermally or photochemically or by redox initiation.
Thus, for example, DE 3407087 C2 discloses scratch-resistant coatings which form as a result of hydrolytic condensation of a mixture which comprises, inter alia, a hydrolyzable titanium or zirconium compound and a hydrolyzable organofunctional silane R′
m
(R″Y)
n
SiX
(4−m−n)
, where R′ is, for example, alkyl or alkenyl, R″ is, for example, alkylene or alkenylene and X is a hydrolyzable radical.
DE 3536716 A1 discloses, for example, adhesives and sealing compounds which have been obtained by hydrolytic condensation of one or more organosilanes of the general formula R
m
SiX
4−m
and, if desired, one or more of the components SiX
4
and/or R
n
(R″Y)
p
SiX
4−n−p
, where R and R″ are, for example, alkyl, alkenyl, aryl, alkylaryl, arylalkyl, alkenylaryl or arylalkenyl, X is, for example, hydrogen, halogen, hydroxyl, alkoxy or acyloxy and Y is, for example, a halogen or an optionally substituted amino, amido, aldehyde, alkylcarbonyl, carboxyl, hydroxyl, mercapto or cyano group.
Furthermore, commercial silanes having reactive double bonds, such as, for example, (meth)acryloyloxysilanes of the following type
where R is hydrogen or methyl and X is, for example, halogen or alkoxy, are known. These silanes are hydrolyzable and polymerizable and can be used for the preparation of the abovementioned systems. They have the major advantage that the resulting coating, the resulting filler, adhesive or sealing compound or the resulting molding can be cured by polymerization at the reactive double bond, thermally, photochemically or by redox initiation.
Commercial silanes having reactive double bonds, such as, for example, the abovementioned (meth)acryloyloxysilanes, are in general monofunctional compounds having a C═C double bond and as a rule have a low molecular weight and, prior to the Si—X hydrolysis and condensation, are therefore relatively volatile compounds which are toxicologically unsafe owing to the acryloyl group present. In the further processing by polymerization or modified functionalization, these silanes also have the disadvantage that, owing to the presence of only one C═C double bond, only chain polymers are obtainable and, in the case of prior functionalization, this C═C double bond necessary for the organic polymerization is generally lost. Furthermore, as a rule only a short chain is present between the double bond and the silicon capable of forming an inorganic network, so that the mechanical properties (flexibility, etc.) can be varied only within narrow limits via the organic groups.
Although DE 4011044 C2 and DE 4416857 C1 disclose hydrolyzable and polymerizable silanes which have more than one reactive C═C double bond and in which the distance between the reactive double bond and the silicon capable of forming an inorganic network is longer, there is still a need for an improvement, also with respect to the functionalization of the molecule.
It is therefore an object of the present invention to provide novel, organically modified silanes which are hydrolyzable and polymerizable and which, alone, as mixtures or together with other hydrolyzable, condensable or polymerizable components, can be processed to give scratch-resistant coatings, fillers, adhesives or sealing compounds, moldings or embedding materials. These silanes should be capable of being used universally and it should be possible to incorporate them in an inorganic-organic composite system, i.e. in an inorganic-organic network. Furthermore, these silanes should be capable of being prepared rapidly and simply, i.e. without a complicated synthesis process. Furthermore, the distance between silicon and reactive double bond should be freely adjustable, and the silane should moreover have a plurality of C═C double bonds.
This object is achieved by hydrolyzable and polymerizable silanes of the general formula I
in which the radicals and indices have the following meaning:
B=straight-chain or branched organic radical having 2 to 50 carbon atoms and at least one C═C double bond, the —CO—NH— group being bonded to a carbon atom of the radical B, and B containing no norbornene, bicyclo[2.2.2]oct-2-ene or 7-oxabicyclo[2.2.1]hept-2-ene group;
R=optionally substituted alkyl, alkenyl, aryl, alkylaryl or arylalkyl, each having 1 to 15 carbon atoms, it being possible for these radicals to contain oxygen and/or sulfur and/or nitrogen atoms;
R
o
=optionally substituted alkylene, alkenylene, arylene, alkylenearylene or arylenealkylene, each having 1 to 15 carbon atoms, it being possible for these radicals to contain oxygen and/or sulfur and/or nitrogen atoms;
R′=optionally substituted alkylene, alkenylene, arylene, alkylenearylene or aryleneakylene, each having 1 to 15 carbon atoms, it being possible for these radicals to contain oxygen and/or sulfur and/or nitrogen atoms;
X=hydrogen, halogen, hydroxyl, alkoxy, acyloxy, alkylcarbonyl, alkoxycarbonyl or NR″
2
, where R″ is hydrogen, alkyl or aryl;
a=1, 2 or 3;
b=1, 2 or 3, and a+b=2, 3 or 4;
c=0 or 1;
d=1, 2, 3, 4, 5, 6, 7, 8, 9 or 10;
e=1, 2, 3 or 4, where e=1 when c=0.
The silanes of the formula I are polymerizable via the radicals B and hydrolyzable via the radicals X. An inorganic network with Si—O—Si units can be built up via hydrolyzable groups, while an organic network can be built up by the polymerization of the double bond(s) contained in the radical B.
In preferred embodiments of the silanes according to the invention, the indices b and/or d and/or e=1. Compounds of the formula Ia result when d=1, those of the formula Ib when e=1, those of the formula Ic when b=1, those of the formula Id when b=e=1, those of the formula Id when d=e=1, those of the formula If when b=d=1 and those of the formula Ig when b=d=e=1.
The alkyl radicals are, for example, straight-chain, branched or cyclic radicals having 1 to 15, in particular having 1 to 10, carbon atoms and preferably lower alkyl radicals having 1 to 6, particularly preferably having 1 to 4, carbon atoms. Specific examples are methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, n-hexyl, cyclohexyl, 2-ethylhexyl, dodecyl and octadecyl. The hydrogen atoms of the alkyl radical may also be substituted by other atoms or groups.
The alkenyl radicals are, for example, straight-chain, branched or cyclic radicals having 2 to 15, preferably having 2 to 10, carbon atoms and preferably lower alkenyl radicals having 2 to 6 carbon atoms, such as, for example, vinyl, alkyl and 2-butenyl.
Preferred aryl radicals are phenyl, biphenyl and naphthyl. The alkoxy, acyloxy, alkylamino, dialkylamino, alkylcarbonyl, alkoxycarbonyl, arylalkyl, alkylaryl, alkylene and alkylenearylene radicals are preferably derived from the abovementioned alkyl and aryl radicals. Specific examples are methoxy, ethoxy, n-propoxy and isopropoxy, n-, iso-, sec- and tert-butoxy, monomethylamino, monoethylamino, dimethylamino, diethylamino, N-ethylanilino, acetyloxy, propionyloxy, methylcarbonyl, ethylcarbonyl, methoxycarbonyl, ethoxycarbonyl, benzyl, 2-phenylethyl and tolyl.
The alkylene, arylene, alkylenearylene and arylenealkyle

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