Organic compounds -- part of the class 532-570 series – Organic compounds – Silicon containing
Reexamination Certificate
2001-04-04
2001-11-20
Shaver, Paul F. (Department: 1621)
Organic compounds -- part of the class 532-570 series
Organic compounds
Silicon containing
C427S387000
Reexamination Certificate
active
06320066
ABSTRACT:
The present invention relates to water-soluble oligomeric and polymeric alkoxysilane compounds having both urea and amino groups, a process for the preparation thereof and the use thereof for surface modification of solids, in particular for coupling on glass surfaces and for sizing of glass fibres.
The use of functional mono-, bis- and tris-alkoxysilanes for coupling and modification of hydroxy-functional surfaces, specifically glass surfaces, is known (Kirk-Othmer, Encyclopedia of Chemical Technology, Vol. 20, 3rd Ed., J. Wiley, N.Y.). Here, the view generally adopted is that coupling arises as a result of hydrolysis of the alkoxysilane groups to silanol groups and as a result of condensation with hydroxyl groups of the surface (E. Pluedemann, Silane Coupling Agents, Plenum Press, N.Y. 1982).
Alkoxysilanes which have an additional functional group able to form further specific or non-specific bonds are preferably used. For example, alkoxysilanes having methacrylic, acrylic, vinyl, amino or urea groups are used. Functional alkoxysilanes able to form further covalent bonds by way of the reaction of the amino group for example with epoxides, carboxylic acids, isocyanates, carboxylic anhydrides, etc., are particularly preferred. These covalent bonds contribute in particular to coupling and bonding to glass surfaces. Examples of these are in particular amino alkoxysilanes and aminoalkylamino alkoxysilanes (U.S. Pat. No. 2,971,864, U.S. Pat. No. 3,234,159).
Aminosilanes, for example 3-aminopropyl trialkoxysilane and N-aminoethyl-3-aminopropyl trialkoxysilane, are commercial products of, for example, Hüls AG, Marl.
The coupling capability is evidently particularly good if oligomeric or polymeric alkoxysilanes having per molecule more than one alkoxysilane group and additionally further reactive functional groups are used. Examples of these are: amino-amido-functional polymers or oligomers having alkoxysilane groups in the side position (U.S. Pat. No. 3,445,441, U.S. Pat. No. 3,746,738, U.S. Pat. No. 4,1263,073) or polyesters having alkoxysilane side groups (EP 43 109). In U.S. Pat. No. 4,244,844 these materials are presented as advantageous for application from aqueous solutions. However, these products have a yellow to brown coloration which is undesirable for industrial applications.
U.S. Pat. No. 4,163,073 and EP 43 109 describe polyesters having amino groups and alkoxysilane groups attached to the main chain of unsaturated polyesters.
It is furthermore known that alkoxysilanes which comprise urea groups are advantageous for coupling on glass surfaces (Progr. Colloid Polym. Sci. 1997, 105: 80-84).
FR 2 678 936 describes polyurea polyurethane macromers terminating in alkoxysilane groups. These compounds comprise more than one alkoxysilane group per molecule and no free amino groups.
Polyurethane prepolymers terminating in bis-functional alkoxysilane groups emerge from U.S. Pat. No. 4,374,237. These compounds comprise alkoxysilane groups in the terminal position as well as urea groups and no free amino groups.
3-Ureidopropyl trialkoxysilanes are, for example, commercial products from Hüls AG, Marl. The preparation and use of ureidosilanes are described in U.S. Pat. No. 4,626,560, U.S. Pat. No. 3,754,971 and U.S. Pat. No. 4,046,794, and the use thereof in WO 94/13473. These silanes, in terms of the alkoxysilane groups to be regarded as monofunctional compounds, have one alkoxysilane group with a maximum of three hydrolysable alkoxy groups or three hydroxy groups per molecule. Such silanes have less good properties than those coupling agents having more than just one alkoxysilane group per molecule.
Ureidosilanes are prepared from monoisocyanate-functional alkoxysilanes by reaction with amines in U.S. Pat. No. 3,493,461. According to EP 406 160 urea alkoxysilane compounds are prepared from mono-, bis-, tris- and higher-functional isocyanates with amino alkoxysilanes. UV-curable or polymerizable oligomers terminating in urea groups, which are functionalised with alkoxysilane groups emerge from WO 94/09013. The adhesive strength of these compounds is very markedly limited by the lack of free amino groups.
Oligomeric and polymeric alkoxysilane compounds which can be applied from water have proved to be advantageous for the purpose of coupling. The water simultaneously activates the alkoxysilane compounds by initiating hydrolysis to the reactive silanol groups.
In the case of amino alkoxysilanes therefore particular importance is accorded to those derivatives which are water-soluble or can be applied from the aqueous phase. These derivatives play a particular part in the coating of glass fibres or the formulation of water-based coupling agents.
EP 406 106 describes alkoxysilane compounds having urea groups, which have been developed for the purpose of miscibility with moisture-curing PU systems and whose amino groups have been further reacted-off by imino or aminal groups, such that no reactive amino groups are present. The coupling of these compounds is limited thereby.
The object was therefore to provide and produce suitable colourless oligomeric or polymeric coupling agents for oxidic surfaces, which can be applied from aqueous solvents.
It has surprisingly been found that the reaction of diamino alkoxysilanes such as, for example, N-aminoethyl-3-aminopropyl trialkoxysilane, with diisocyanates leads to uncross-linked, soluble linear urea oligomers and urea polymers having free amino groups in the terminal position and alkoxysilane groups in the side position, which are stable in storage in organic solution, and which afford stable solutions in aqueous solvents. In particular the combination of free amino groups, urea groups and more than one alkoxysilane group per molecule in this case leads to excellent properties.
The present invention provides water-soluble oligomeric or polymeric amino-functional urea alkoxysilane compounds obtainable by reacting
a) from 1 to 1.8 equivalents of a diisocyanate with
b) 2 equivalents of a diamine consisting of
b1) from 80 to 100 wt. % of a diamino alkoxysilane of the formula (I)
HN(R
1
)—Z—N(H)—Y—Si(OR
2
)
(3−a)
R
3
a
(I)
wherein
Z denotes C
1
-C
6
-alkylene, C
5
-C
10
-cycloalkylene or arylene,
R
1
denotes H, C
1
-C
6
-alkyl or C
5
-C
10
-cycloalkyl,
Y denotes C
3
-C
6
-alkylene,
R
2
denotes C
1
-C
6
-alkyl or C
5
-C
10
-cycloalkyl,
a is from 0 to 2, and
R
3
denotes C
1
-C
6
-alkyl or C
5
-C
10
-cycloalkyl, and
b2) from 0 to 20 wt. % of at least one nonionic hydrophilic compound comprising ether groups and having per molecule two groups capable of reacting with isocyanate groups, in particular hydroxyl and/or amino groups.
Aromatic, aliphatic, heterocyclic, monocyclic and polycyclic bifunctional isocyanate compounds are preferably suitable as diisocyanates.
Diisocyanates of the formula (II)
OCN—R—NCO (II)
may preferably be used wherein
R denotes C
1
-C
6
-alkylene, C
5
-C
15
-cycloalkylene, C
6
-C
14
-arylene, C
7
-C
20
-arylalkylene or C
7
-C
20
-alkylarylene.
Diisocyanates of the ethylene diisocyanate type, 1,2-diisocyanatopropane, 1,3-diisocyanatopropane, 1,4-butylenediisocyanate (BDI), 1,6-diisocyanatohexane (HDI), 1,2-diisocyanatocyclohexane, 1,3-diisocyanatocyclohexane, 1,4-diisocyanatobenzene, bis(4-isocyanatocyclohexyl) methane (H12MDI), bis(4-isocyanatocyclohexenyl) methane, bis(4-isocyanatophenyl) methane (MDI), 2,4- and 2,6-toluene diisocyanate (TDI), 1,5-diisocyanatonaphthalene, hydrogenated toluene diisocyanate, 1-isocyanatomethyl-5-isocyanato-1,3,3-trimethyl cyclohexane (isophorone diisocyanate, IPDI), 1,6-diisocyanato-2,2,4-tnimethyl hexane are preferred.
1,6-diisocyanatohexane and 1-isocyanatomethyl-5-isocyanato-1,3,3-trimethyl cyclohexane (isophorone diisocyanate) are particularly preferred.
Furthermore isocyanates which are on average bis-functional, which have been prepared by reaction or oligomerisation of diisocyanates, can preferably be used. Thus for example, products comprising allophanate, uretdione or biuret groups (such as, for example, Desmodur® N100 from Bayer AG, Leverkusen) or pa
Audenaert Raymond
Joachimi Detley
Karbach Alexander
Simon Joachim
Bayer Aktiengesellschaft
Gil Joseph C.
Preis Aron
Shaver Paul F.
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