Organosiloxanyl derivatives of alkanediol monovinyl ethers,...

Details Organosiloxanyl derivatives of alkanediol monovinyl ethers,... Organosiloxanyl derivatives of alkanediol monovinyl ethers,...

1997-06-04

2001-10-02

Mullis, Jeffrey C. (Department: 1711)

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

Synthetic resins

Mixing of two or more solid polymers; mixing of solid...

C525S475000, C525S479000, C528S026000, C528S010000, C528S028000, C528S025000, C528S029000, C528S031000, C528S033000

Reexamination Certificate

active

06297331

ABSTRACT:

BACKGROUND OF THE INVENTION
The invention relates to novel organosiloxanyl derivatives of alkanediol monovinyl ethers, to a process for preparing these derivatives, to the use thereof for preparing organomodified siloxanes and to the use thereof as paint additives.
Hydroxyalkyl-functional polysiloxanes are commercially available (e.g. Tegopren HSi 2111, Th. Goldschmidt AG) and can easily be prepared industrially by known methods. Compounds of this kind are used, for example, as starting materials for the synthesis of silicone polyesters (U.S. Pat. No. 5,488,123). Likewise in accordance with the prior art are processes for preparing organopolysiloxanes which have on average at least one terminal or lateral group —(CH
2
)
3
OCH
2
CH(X)CH
2
OH, in which X can, for example, be a hydroxyl, alkoxy or amine group (DE-C-32 15 317).
In the course of these reactions of hydrogensiloxanes with 1-alkenyl alcohols, however, a side reaction which occurs is the unwanted rearrangement into the 2-alkenol, which is unreactive for hydrosilylations. Consequently, it is usually necessary in the case of such hydrosilylation reactions to employ a high excess of the alkenols, which is removed again by distillation after the end of the reaction. As is known, this problem is also encountered in the hydrosilylation reaction of hydridosiloxanes with allyl alcohol alkoxylates (U.S. Pat. No. 4,083,856). Here too, propenyl polyethers which are formed after rearrangement of the double bond withdraw almost completely from the hydrosilylation reaction and remain in the reaction mixture. As a result it is necessary first of all, in order to achieve complete conversion of the Si—H component, to start from an excess of the olefin component; in certain cases such excesses may be in the range of up to 50 mol percent. To prepare the pure hydrosilylation adducts it would also be necessary here to purify the reaction product by distillation to remove the rearrangement product. However, such purification, especially in the case of olefin components of relatively high molecular mass, is not technically feasible.
The use of 1,4-butanediol monovinyl ether as an adduct with silanes has already been mentioned in U.S. Pat. No. 5,384,342. In that document, however, the linkage is formed by way of a silicon-oxygen bond, so that the free double bond remains available for UV-induced crosslinking reactions. In this way, however, no hydroxyalkyl-functional silane derivatives are formed.
SUMMARY OF THE INVENTION
The present invention, then, provides organosiloxanyl derivatives with ethyl hydroxyalkyl ether attached via carbon to silicon and their preparation and provides for their use as paint raw materials and for their use as intermediates for the preparation of silicone polyethers, silicone polyesters, silicone polyurethanes, silicone acrylates and silicone isocyanates.
The compounds of the present invention, then, are of the general formula:
in which
R
1
=identical or different aliphatic or aromatic hydrocarbon groups,
R
2
=CH
2
CH
2
O(CR
4
R
5
)
x
OH, where
R
3
=R
2
or R
1
,
a=1 to 50 and
b=0 to 500.
It is familiar to the expert that the compounds exist in form of a mixture of oligomers having a distribution which is governed essentially by statistical laws. The values of a and b are, consequently, mean values.
Compounds of this kind are in turn, for example, useful raw materials for further-prior art-reactions to give follow-on products. Among such reactions, primary mention should be made of reactions giving silicone polyethers, silicone polyesters, silicone polyurethanes, silicone acrylates or silicone isocyanates.
The novel organosiloxanyl derivatives are readily obtainable by way of transition metal catalyzed hydrosilylation reactions of organosiloxanyl derivatives with alkanediol monovinyl ethers.
They can be prepared in a simple manner such as, for example, by subjecting hydrogen-functional siloxanes of the general formula:
in which
R
1
=identical or different aliphatic or aromatic hydrocarbon groups,
R
2
=H
R
3
=R
2
or R
1
,
a=1 to 50 and
b=0 to 500;
to an addition reaction with alkanediol monovinyl ethers of the general formula:
in which
R
4
and R
5
can be identical or different groups and are each a H or an alkyl group, branched or unbranched, having up to a total of 12 carbon atoms, and x has a value from 2 to 11, in the presence of a conventional hydrosilylation catalyst (platinum or rhodium catalyst).
Preferred examples of the groups R
4
and R
5
are hydrogen and alkyl groups from C1 to C8. More preferably, R
4
and R
5
are hydrogen. Preferably, x is the value of from 2 to 6. More preferably, x=4.
In the course of the hydrosilylation reaction with alkanediol monovinyl ethers it has been found, surprisingly, that no excess of the olefinic component is necessary in such reactions but that this component can be employed in an amount equimolar with the SiH component, since the rearrangement of the double bond (for example in the case of allyl groups) which otherwise occurs with hydrosilylation reactions is ruled out in the case of the vinyl double bond in the examples described.
Examples of novel substances of the present invention are:
The siloxanes employed for the reactions with vinyl hydroxyalkyl ether can, for example, have the following structure:
Compound
a
b
R
1
1
0
Me
2
5
13
Me
3
5
43
Me
4
4.5
20.5
Me
5
25
75
Me
6
10
80
H
7
10
100
Me
The novel organosiloxanyl derivatives, in turn, are valuable starting compounds for further, prior art reactions to give follow-on products. Among such reactions primary mention should be made of reactions giving silicone polyethers, silicone polysters, silicone polyurethanes, silicone acrylates or silicone isocyanates.
Examples of such organomodified organosiloxanes are
The novel compounds and their derivatives can be used, for example, as additives in waterborne, solventborne or powderborne paints or printing inks, and can also be used as deaerating agents, lubricants and leveling agents, etc. Typical concentrations employed are between 0.01 and 15% by weight.
Surprisingly, the use of the novel compounds is particularly suitable for the production of dirt-repellent coatings. They can be used, for example, for producing anti-graffiti coatings.
The problem of graffiti has in recent years confronted the public again and again. In most cases it is public buildings and public transportation vehicles that are affected. Since in the majority of cases removal is not possible by simply washing, costly, labor intensive repainting of the surfaces carrying the graffiti is usually necessary.
Protective coatings comprising fluorine-containing polymers, as described, for example, in U.S. Pat. No. 4,929,666 and U.S. Pat. No. 5,006,624, bring about the dirt-repelling properties through a reduction in the surface tension.
Polysiloxane compounds likewise bring about a reduction in surface tension. For instance, the solution polymers described in DE-A-26 10 372, which are prepared in a mixture of organic solvents and alkylhydrogenpolysiloxanes, are used to impregnate textiles.
Copolymerization of (meth)acrylic monomers with epoxy functions in the presence of silanols produces, in accordance with U.S. Pat. No. 5,077,350, a polymer for powder coatings. Owing to the high reactivity of the silanols employed, which comprise at least two Si—OH functions, copolymerization without the occurrence of gelling is possible only with specific monomers.
EP-A-0 603 561 describes polydimethylsiloxane-containing binders which are obtained by free-radical polymerization of (meth)acrylate monomers in the presence of &agr;,&ohgr;-functional polysiloxanes. Because of the low functionality of the polysiloxanes, it is possible for there to be instances of incompatibility with paint systems, and the systems exhibit inadequate resistance to soiling, as, for example, to felt-tipped pens.
DE-A-35 35 283 describes polyester-functional polysiloxanes for paints and molding compounds. The polysiloxane gives an anti-adhesive character to the

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