Hydrolysable and polymerizable oxetane silanes

Details Hydrolysable and polymerizable oxetane silanes Hydrolysable and polymerizable oxetane silanes

2000-06-09

2001-09-04

Trinh, Ba K. (Department: 1625)

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

Organic compounds

Heterocyclic carbon compounds containing a hetero ring...

C549S510000, C549S511000, C522S168000, C522S172000

Reexamination Certificate

active

06284898

ABSTRACT:

The invention relates to hydrolysable and polymerizable oxetane silanes, a process for the preparation thereof, silicic acid condensates, polymers and compositions prepared therefrom and the use of all these materials inter alia for the preparation of macromolecular compositions by polymerization and for the preparation of composite materials, adhesives, coatings and in particular dental materials.
Hydrolysable silanes, which contain polymerizable organic radicals, are used in the preparation of coatings, particulate fillers, adhesive compositions and monolithic moulded articles and in the surface modification of reinforcing substances. The silanes are hydrolytically condensed and polymerized thermally, photochemically or by redox initiation, i.e. cured, alone, mixed with other silanes or in the presence of other metal alkoxides.
Of particular interest in connection with the preparation of organic-inorganic composite materials are above all organically modified silanes with polymerizable organic groups, such as vinyl, (meth)acrylic, allyl or styryl groups, since they permit the simultaneous or consecutive formation both of an inorganic and of an organic network and therefore of composite materials with customized properties (cf H. Schmidt, Mat. Res. Soc. Symp. Proc. Vol. 32 (1984), 327-335; H. Schmidt, H. Wolter, J. Non-Cryst. Solids 121 (1990) 428-435). The polymerizable silanes are as a rule in the first step hydrolytically condensed in solution. After the addition of thermal initiator or photoinitiator and removal of the solvent, nanoparticulate resins then form which are shaped and then polymerized and thus cured.
A major disadvantage of these materials, however, is that the development of the organic network which takes place on polymerization is mostly accompanied by a considerable volume contraction which may result in deformation of the moulded articles, reduction in substrate adhesion, layer separation, development of voids or development of material stresses. A reduced volume contraction takes place with silanes which bear ring-opening groups. In this connection, EP-B-0 358 011 describes scratch-resistant materials inter alia based on 3-glycidyloxypropyl silanes, EP-B-0 486 469 describes organic-inorganic hybrid polymers of 3-glycidyloxypropyl silanes and DE-C-41 33 494 describes dental resin compositions in which e.g. silanes with ring-opening spiroortho ester groups are used. It proves to be disadvantageous, however, that epoxide silanes are toxicologically unacceptable and cationically polymerize sufficiently quickly at elevated temperatures only. Furthermore, spiroortho ester silanes exhibit only a low stability and their cationic ring-opening polymerization is generally accompanied by the formation of lactone.
Furthermore, the following silicon-containing oxetane derivatives are also known:
1. Silicon-containing oxetanes which are obtainable e.g. by hydrosilylation of 3-allyloxymethyl-3-ethyl-oxetane with 1,1,3,3-tetramethyldisiloxane (cf J. V. Crivello et al., J. Macromol. Sci.-Pure Appl. Chem. A30 (1993), 173-187):
2. 3-(trimethylsiloxy)-oxetanes which can be synthesized by Paterno-Büchi reaction (cf T. Bach, Tetrahedron Lett. 32 (1991), 7037-8):
3. 3-Alkyl-3-(triorganosiloxymethyl)-oxetanes or 3-alkyl-3-(triorganosilylmethyl)-oxetanes (cf DE-A-195 06 222):
4. 3,3-bis(triorganosiloxymethyl)-oxetanes which can be obtained by reacting 3,3-bis(hydroxymethyl)-oxetanes with appropriate triorganoaminosiloxanes R
3
SiNH
2
(cf Chem. Abstr. 76 (192) 14701k):
It is the object of the invention to provide hydrolysable and polymerizable oxetane silanes from which, alone or together with other hydrolytically condensable and polymerizable components, stable compositions can be prepared which polymerize with only low shrinkage and at high speed at room temperature, and which are suitable as composite or coating material, adhesive or adhesion promoter or for the preparation of fillers or materials for medical or dental purposes. These silanes are to be able to be covalently incorporated into organic-inorganic composite materials and be synthetically obtainable so that the distance between silicon and the polymerizable groups can be varied.
This object is achieved according to the invention by the hydrolysable and polymerizable oxetane silanes according to Claims
1
to
3
. The invention further relates to the silicic acid condensates according to Claim
4
, the polymerizates according to Claim
5
, the compositions according to Claims
6
and
7
and the use according to Claim
8
.
The hydrolysable and polymerizable oxetane silanes according to the invention and the stereoisomers thereof correspond to the general formula (I):
in which the variables R
0
, R
1
, R
2
, R
3
, R
4
, R
5
, R
6
, X, Y, a, b, c, and x, unless otherwise stated, independently of one another have the following meanings:
R
0
=hydrogen or substituted or unsubstituted C
1
to C
10
alkyl;
R
1
=missing or represents substituted or unsubstituted C
1
to C
18
alkylene, C
6
to C
18
arylene, C
7
to C
18
alkylenearylene or arylenealkylene, these radicals being able to be interrupted by at least one group selected from ether, thioether, ester, carbonyl, amide and urethane groups;
R
2
=missing or represents substituted or unsubstituted C
1
to C
18
alkylene, C
6
to C
18
arylene, C
7
to C
18
alkylenearylene or C
7
to C
18
arylenealkylene, these radicals being able to be interrupted by at least one group selected from ether, thioether, ester, thioester, carbonyl, amide and urethane groups or being able to bear these in the terminal position;
R
3
=missing or represents substituted or unsubstituted C
1
to C
18
alkyl, C
2
to C
18
alkenyl, C
6
to C
18
aryl, C
7
to C
18
alkylaryl or C
7
to C
18
arylalkyl, these radicals being able to be interrupted by at least one group selected from ether, thioether, ester, carbonyl, amide and urethane groups;
R
4
=missing or represents substituted or unsubstituted —CHR
6
—CHR
6
—, —CHR
6
—CHR
6
—S—R
5
, —S—R
5
—, Y—CO—NH—R
5
— or —CO—O—R
5
—;
R
5
=substituted or unsubstituted C
1
to C
18
alkylene, C
6
to C
18
arylene, C
6
to C
18
alkylenearylene or C
6
to C
18
arylenealkylene, these radicals being able to be interrupted by at least one group selected from ether, thioether, ester, carbonyl, amide and urethane groups;
R
6
=hydrogen or substituted or unsubstituted C
1
to C
18
alkyl or C
6
to C
10
aryl;
X=a hydrolysable group, namely halogen, hydroxy, alkoxy or acyloxy;
Y=O or S;
a=1, 2 or 3;
b=1, 2 or 3;
c=1 to 6; and
x=1, 2 or 3;
and with the proviso that
(i) a+x=2, 3 or 4 and
(ii) a and/or b=1.
However, the above formula covers only those compounds which are compatible with the valency theory.
The silanes according to the invention are usually present as stereoisomer mixtures and in particular as racemates.
The ether, thioether, ester, thioester, carbonyl, amide and urethane groups which are possibly present in the radicals are defined by the following formulae: —O—, —S—, —CO—O—, —O—CO—, —CO—S—, —S—CO—, —CS—O—, —O—CS—, —CO—, —CO—NH—, —NH—CO—, —O—CO—NH— and —NH—CO—O—.
The non-aromatic radicals or non-aromatic parts of the radicals possible in formula (I) can be straight-chained, branched or cyclic.
Alkyl radicals have preferably 1 to 8 and particularly preferably 1 to 4 carbon atoms. Particular examples of possible alkyl radicals are methyl, ethyl, n- and iso-propyl, sec- and tert-butyl, n-pentyl, cyclohexyl, 2-ethylhexyl and octadecyl.
Alkenyl radicals have preferably 2 to 10 and particularly preferably 2 to 6 carbon atoms. Particular examples of possible alkenyl radicals are vinyl, allyl and iso-butenyl.
Preferred examples of possible aryl radicals are phenyl, biphenyl and naphthyl.
Alkoxy radicals preferably have 1 to 6 carbon atoms. Particular examples of possible alkoxy radicals are methoxy, ethoxy, n-propoxyl iso-propoxy and tert-butoxy.
Acyloxy radicals preferably have 2 to 5 carbon atoms. Particular examples are acetyloxy and propi

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