Aminopropyl-functional siloxane oligomers

Details Aminopropyl-functional siloxane oligomers Aminopropyl-functional siloxane oligomers

1999-10-27

2002-05-28

Dawson, Robert (Department: 1712)

Synthetic resins or natural rubbers -- part of the class 520 ser

Synthetic resins

From silicon reactant having at least one...

C528S033000, C528S037000, C556S413000, C556S425000, C556S450000, C556S460000, C556S466000

Reexamination Certificate

active

06395858

ABSTRACT:

BACKGROUND OF THE INVENTION
1. Field of the Invention
The present invention relates to compositions containing mixtures of catenate and cyclic siloxane oligomers of the formulae I and II:
where the R substituents comprise both alkoxy groups and organofunctional groups, and where not more than one organofunctional group is attached to one silicon atom.
The present invention also relates to a process for preparing the mixtures and to their use in a variety of applications.
2. Description of the Background
Mixtures of catenate and cyclic siloxane oligomers are obtained, for example, by controlled hydrolysis or condensation of organofunctional alkoxysilanes. A particular problem when preparing multifunctional siloxane oligomers is the highly differing hydrolysis or condensation behavior of the individual organoalkoxy or organochlorosilanes.
EP 0 716 128 A2, EP 0 716 127 A2 and EP 0 675 128 2 A1 disclose aqueous solutions of amino-functional and CH-containing organosilanes and organosiloxanes. In these organosilane systems, hydrolysis is virtually complete.
EP 0 518 057 A1 and DE 196 24 032 A1 disclose mixtures of catenate and cyclic vinyl- and also alkyl-functional siloxane oligomers which also carry alkoxy groups. Such mixtures are employed, for example, to hydrophobicize mineral surfaces and pulverulent substances, and as crosslinking agents for thermoplastic polyolefins.
German patent application serial number 198 34 990.4 describes mixtures of catenate and cyclic acryloxypropyl- or methacryloxypropyl-functional siloxane oligomers.
Such siloxane oligomer mixtures can be used, for example, for the surface treatment of mineral surfaces or pulverulent substances, such as titanium dioxide, talc, clay, silicas, quartz, kaolin, aluminum hydroxide, magnesium hydroxide, bentonite, montmorillonite, mica (muscovite mica), calcium carbonate (chalk, dolomite), for example. These siloxane oligomer mixtures are also employed as adhesion promoters in, for example, kaolin-filled rubber compounds.
However, there still remains a need for new compositions containing siloxane oligomers.
SUMMARY OF THE INVENTION
It is an object of the present invention to provide novel organofunctional siloxane oligomer mixtures, containing amino-functionalized siloxane compounds.
It is another object of the invention to provide methods of making the mixtures.
It is another object of the invention to provide methods of using the mixtures for a variety of purposes.
The objects of the invention, and others, may be accomplished with a mixture of catenate and cyclic siloxane oligomers of the formulae I and II:
where the substituents R are
(i) aminopropyl-functional groups of the formula —(CH
2
)
3
—NH
2
or —(CH
2
)
3
—NHR′ or —(CH
2
)
3
—NH(CH
2
)
2
—NH
2
or —(CH
2
)
3
—NH(CH
2
)
2
—NH(CH
2
)
2
—NH
2
, in which R′ is a linear, branched or cyclic alkyl group of 1 to 18 carbon atoms or an aryl group of 6 to 12 carbon atoms, and
(ii) methoxy, ethoxy, 2-methoxyethoxy and/or propoxy groups, and
(iii) if desired, alkyl, alkenyl, isoalkyl or cycloalkyl groups of 1 to 18 carbon atoms and/or aryl groups of 6 to 12 carbon atoms,
where
not more than one aminopropyl-functional group is attached to one silicon atom,
the degree of oligomerization of compounds of the formula I is within the range 2<m<30 and that of compounds of the formula II is 3≦n≦30, and the quotient of the molar proportion of Si/alkoxy group is ≧0.5.
Such mixtures may be obtained by a controlled reaction using at least one aminopropyl-functional trialkoxysilane or one aminopropyl-functional methyldialkoxysilane as component A and, if desired, at least one alkyl-, alkenyl-, isoalkyl- or cycloalkyl-trialkoxysilane of 1 to 18 carbon atoms and/or phenyltrialkoxysilane and/or alkyl-, alkenyl-, isoalkyl- or cycloalkyl-methyldialkoxysilane of 1 to 18 carbon atoms and/or phenylmethyldialkoxysilane as component B and, if desired, a tetraalkoxysilane as component C, subjecting the components A and—if used—B and C in succession or in a mixture to controlled hydrolysis and condensation using from 0.6 to 1.2 mol. of water per mol. of Si and from 0.1 to 5 times the amount by weight of methanol and/or ethanol, based on the alkoxysilanes employed, at a temperature from 10 to 95° C. and subsequently working up the product mixture by distillation under atmospheric pressure or under reduced pressure and at a liquid-phase temperature of up to 120° C. In the course of this distillation the free alcohol and any residues of the unhydrolyzed monomeric starting materials are suitably removed from the product. It is possible, accordingly, to provide a further amino-functional siloxane oligomer mixture. A particular advantage is that the hydrolysis or condensation can be carried out in a controlled manner without an additive alien to the system, such as a hydrolysis or condensation catalyst.
The objects of the present invention may also be accomplished with methods of using the compositions containing the siloxane mixtures described above. Such methods of use include the following:
(1) a method of improving the adhesion properties of adhesives and sealants, by incorporating the composition into an adhesive or a sealant,
(2) a method of modifying organic resins, by contacting an organic resin with the composition,
(3) a method of crosslinking organic resins, by contacting the organic resins with the composition,
(4) a method of providing binders in inks and coatings, by incorporating the composition into an ink or a coating,
(5) a method of coating glass fibers, by applying the composition to glass fibers,
(6) a method of promoting adhesion in filled thermoplastic compounds, by incorporating the composition into the filled thermoplastic compounds,
(7) a method of treating mineral, organic and metallic surfaces, by applying the composition to a mineral, organic or metallic surface,
(8) a method of hydrophobicizing surfaces, by applying the composition to a surface, and
(9) a method of surface modifying pulverulent substances, by applying the composition to the surface of a pulverulent substance.
A more complete appreciation of the invention and many of the attendant advantages thereof will be readily obtained as the same becomes better understood by reference to the following detailed description.
DETAILED DESCRIPTION OF THE INVENTION
Resultant mixtures of the invention comprising catenate and cyclic siloxane oligomers are normally homogeneous, clear, colorless to pale yellow liquids of low viscosity which are stable on storage and preferably have a flash point>100° C.
By means of the procedure described above it is possible advantageously to produce siloxane oligomers of the invention possessing, preferably, a statistical distribution of [—Si(R)(R)O—] units of different functionality.
It is also advantageous that the boiling point of the mixtures of the invention comprising catenate and cyclic siloxane oligomers is generally at a temperature >200° C.
The present invention therefore provides a mixture of catenate and cyclic siloxane oligomers of the formulae I and II:
where the substituents R consist of
(i) aminopropyl-functional groups of the formula —(CH
2
)
3
—NH
2
or —(CH
2
)
3
—NHR′ or —(CH
2
)
3
—NH(CH
2
)
2
—NH
2
or —(CH
2
)
3
—NH(CH
2
)
2
—NH(CH
2
)
2
—NH
2
, in which R′ is a linear, branched or cyclic alkyl group of 1 to 18 carbon atoms or an aryl group of 6 to 12 carbon atoms, and
(ii) methoxy, ethoxy, 2-methoxyethoxy and/or propoxy groups, and
(iii) if desired, alkyl, alkenyl, isoalkyl or cycloalkyl groups of 1 to 18 carbon atoms and/or aryl groups of 6 to 12 carbon atoms,
and where not more than one aminopropyl-functional group is attached to one silicon atom and the degree of oligomerization of compounds of the formula I is within the range 2<m<30 and that of compounds of the formula II is 3≦n≦30 and the quotient of the molar proportion of Si/alkoxy group is ≧0.5.
Thus, each R is independently selected from the group consisting of —CH
2
)
3
—NH
2
, —(CH
2
)
3
—NHR′, —CH
2
)
3
—NH(CH
2
)
2
—NH
2
,

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