JPS6017797B2 - Production method of organopolysiloxane - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION It is already known that an organosilanol and an isocyanate are reacted to form an organosilicon compound having a substituted carbamyloxy group (triSiOCO-NH-) bonded to silicon via oxygen. It has also been introduced that a polysiloxane having Si-bonded hydroxyl groups is reacted with a divalent or trivalent isocyanate (UK Patent No. 888938, publication date: February 7, 1962, Imperial Chemical Ltd. tr
ies).

Polysiloxane is organopolysiloxane or SI
If it is a polysiloxane with C-bonded organic groups and not an alkoxypolysiloxane such as di-ten-butoxypolysiloxane, an organopolysiloxane with carbamoyloxy groups will not be obtained when reacted with isocyanate. Rather, either no reaction occurs, or water is simply eliminated from the Si-bonded hydroxyl group of the organopolysiloxane, increasing the viscosity of the organopolysiloxane.
On the other hand, in the process of the present invention, an organopolysiloxane having a substituted carbamoyloxy group bonded to silicon via oxygen is obtained. A process for the preparation of organopolysiloxanes having hydroxyl groups, which comprises an organopolysiloxane having at least one Si-bonded hydroxyl group and at least one monovalent or polyhydric organic isocyanate as the only reactant. It consists of reacting in the presence of a compound.

For example, West German Patent Publication No. 1769666 (
Published: 197th place King December 3rd, DowComingCo
rp. , which corresponds to Canadian Patent No. 83252 and French Patent No. 1572724) and West German Patent No. 2135673 (
Published on 1st February 1973 by &yer AG, which publication corresponds to British Patent No. 134222y), materials for producing adhesive-repellent coatings are known; In addition to mixing organopolysiloxanes with Si-bonded hydroxyl groups with isocyanates and organotin compounds, silicate esters and organopolysiloxanes with Si-bonded hydrogens or acetoxysilanes are also added as further substances.

It is not previously known that this material or the coatings produced therefrom contain olga/polysiloxanes with substituted carbamoyloxy groups bonded to silicon via oxygen. The organoborisiloxanes having at least one Si-bonded hydroxyl group used in the process according to the invention are preferably diorganosiloxane units, molar organosiloxane units, triorganosiloxane units, Si04'2-units or at least two of said units. However, of course, Si
The number of 04'2 units is at most diorganosiloxane units, monoorganosiloxane units and/or triorganosiloxane units.
of the same size as the number of siloxane units, at least one of the siloxane oxygen atoms per each molecule must be replaced by a hydroxyl group and each molecule contains at least 2 siloxane units, preferably at least 3 siloxane units. .

The number of siloxane units may be 1000 or more per molecule. Furthermore, all silicon valencies not saturated by SIC combined organic groups and hydroxyl groups are saturated by siloxaso oxygen atoms, and at least two diorganosiloxane units and/or at least two Si- It is advantageous for the number of triorganosiloxane units optionally present to be smaller than the number of molar organosiloxane units optionally present, since they have bound hydroxyl groups and are particularly readily available.
In the process according to the invention, in each case one Si-bonded hydride is used as organopolysiloxane having at least one Si-bonded hydroxyl group in the terminal unit. Particular preference is given to diorganopolysiloxanes containing xyl groups. The monoorganosiloxane unit has the formula RSiC3'2,
Diorganosiloxane units are represented by the formula i0, and triorganosiloxaso units are represented by the formula Ri○,/2.

Within the scope of the process according to the invention, R in all these formulas represents the same or different monovalent hydrocarbons, which may also carry substituents inert towards the isocyanate, in particular fluorine and/or chlorine. The organic group in the organopolysiloxane used in the present invention has 1 to 1 carbon atom per group.
Advantageously there are twelve. Examples of the organic group, thus the hydrocarbon group R, in the organopolysiloxane used in the present invention are alkyl groups, such as methyl group, ethyl group, n
-Propyl group, isof0.

Pyr, n-butyl and sec-butyl as well as octyl and dodecyl groups; cycloalkyl groups such as cyclobentyl, cyclohexyl and cycloheptyl; alkenyl groups such as vinyl and allyl; aryl groups such as phenyl ; an alkaryl group, such as a tolyl group; and an aralkyl group, such as a penzyl group. Examples of substituted hydrocarbon radicals R are the 1.111-trifluoropropyl and Q.Q.Q-trifluorotolyl groups and the chlorphenyl and diclophenyl groups. However, for reasons of availability, it is advantageous for at least 80% of the organic groups, and thus the number of radicals R, of the organopolysiloxanes used in the invention to be methyl groups. If the isocyanate used in this invention is polyvalent, it has a maximum of 1 isocyanate group per molecule.

The isocyanates used in the present invention may be monomeric compounds and/or prepolymers. Examples of isocyanates that can be used according to the invention are phenyl isocyanate, p-ethoxyphenylisocyanate, 01, m-
and p-tolyl isocyanate, naphthylene diisocyanate, diphenylmethane-4,4'-diisocyanate, tolylene diisocyanate, triphenylmethane-4,4',4''-triisocyanate and polyphenylpolymethylene polyisocyanate, and "desmodyur" ( Toluylene diisocyanate obtained under the name DeSmodur® L” and 1.1.
It is a reaction product obtained from 1-trimethylolpropane. Many other examples of polyvalent isocyanates that can be used in all of the present inventions include U.S. Pat.
It is described in Specification No. 6 (late W.V. NJN et al., Yer AG). Preference is given to polyvalent isocyanates, especially those having 2 or 3 isocyanate groups per molecule.

It is advantageous to use the isocyanate in an amount of at least 1 gram mol of isocyanate groups per gram mol of Si-bonded hydroxyl groups.

More than 100 gram moles of isocyanate groups can be used per gram mole of Si-combined hydroxyl groups. Examples of organotin compounds are di-n-butyltin diacetate, di-n-butyltin dilaurate, di-n-butyltin oxide, tin(0)-2-ethylhexoate, mixtures of di-n-butyltin diacylate, In fact, the acylate groups each have 9 to 11 carbon atoms per molecule, - parentheses where the carboxyl groups are present in at least 9% by weight of the acid.
di-n-butyl-di-2-ethylhexoate and cistanoxanes, such as diacetoxytetra-2-butyldistanoxane and dioleoyltetramethyldista It is Noxane.

A variety of organotin compounds can be used if desired. Di-n-butyltin dilaurate is preferred. It is advantageous to use the organotin compound in an amount of 0.001 to 5% by weight, based on the weight of the respective amount of organopolysiloxane used containing at least one Si-bonded hydroxyl group.

At least one Si
- the use of at least one solid organotin compound in the reaction of an organopolysiloxane having bound hydroxyl groups with an organic isocyanate and the use of koji with exclusion of water for the removal of the catalyst; It is advantageous to be treated as such.

Activated carbon is preferred as solid carrier.

Other examples of supports that can be used within the scope of the invention include silicon dioxide, aluminum oxide, graphitic carbon, silicon carbide, clays, bentonites, and zeolites. The solid carrier should be used in as anhydrous form as possible and should react neutrally. 5 to 50 parts by weight, especially 10 parts by weight, of an organotin compound are added to each solid carrier.
Advantageously, it is used in an amount of ˜15 parts by weight. The organotin compound can be supported on the rod in a solvent inert to the organotin compound, such as acetone, and the solvent can then be evaporated. This evaporation can be carried out under reduced pressure. When carrying out the process of the invention, anhydrous solvents that are inert to the reaction components and reaction products can be used.

Examples of suitable solvents are hydrocarbons such as toluene, halogenated hydrocarbons such as velchlorethylene and methylene chloride, esters such as ethyl acetate, and ethers such as tetrahydrofuran, di-n-butyl ether or dioxane. Mixtures from different solvents can be used if desired. The method according to the invention can be carried out at room temperature
It is advantageous to carry out the process at a temperature in the range of 150°C.

Since minimum expenditure is required, it is advantageous to carry out the process according to the invention at ambient atmospheric pressure, ie 1 bar. Higher or lower pressures can be used if desired. The process according to the invention can be carried out with agitation of the reaction components, for example by milling or rolling, and also batchwise, semi-continuously or completely continuously. The solid support may be mobile or placed in a fixed bed. The compounds obtained according to the invention can be obtained by using an excess of isocyanate having 1 to 1 isocyanate groups, at least one group [wherein a is an integer from 1 to 9 and A is one or more of the organic groups used]. represents an organic group to which isocyanate groups are bonded].

The compounds obtained according to the invention can be used, for example, as lubricants for organic and inorganic fibers, as materials for the production of coatings, e.g. on glass, as materials for improving the gloss and feel of synthetic and natural leathers and for the production of polyurethanes. Or it is suitable as an additive during processing.

The present invention will now be explained in more detail with reference to examples, in which all "%" are "% by weight" unless otherwise stated.

Example 1 Dimethylpolysiloxane 200 with one Si-bonded hydroxyl group in each terminal unit, an average of about 1 silicon atom per molecule, and a refractive index of 1.404.
A mixture of about 80% of 2,4-toluylene diisocyanate and about 20% of 2,6-toluylene diisocyanate was prepared by suspending 11.76% of activated carbon in 200% of triol and 100% of acetone. One day of di-butyltin dilaurate was added to the cloudy solution, the acetone was removed, and the mixture was dried and mixed with the prepared mixture.

The mixture thus obtained is boiled under reflux for 1 hour. After cooling the mixture to room temperature, it is filtered with exclusion of water. After the toluol was distilled off, the oak liquor was clear and slightly yellow with a refractive index of 1.
．． It is an oily substance with a molecular weight of 417. A 50% solution of this oil in triol remains unchanged for several weeks with exclusion of water.

Upon introduction of water vapor contained in the air, this solution decomposes with the evolution of gas and the formation of a solid substance. Example 2 “Desmodur (registered trademark) L”
Toluylene diisocyanate and 1
- A 75% solution of the reaction product from 1,1-trimethylolpropane in ethyl acetate 1,000.5 ml, first 450 ml of ethyl acetate, then di-2-butyl ether. 5 days, then a mixture of activated carbon and di-n-butyltin dilaurate (preparation is described in Example 1) 19.5 days, and finally a mixture of activated carbon and di-n-butyltin dilaurate, each with one Si-bonded hydroxyl group in the terminal unit. Thirty minutes of dimethylborisiloxane having an average of about one silicon atom per molecule is added.

The mixture thus obtained is boiled under reflux for 1 hour. After cooling the mixture to 50° C., it is passed under water exclusion. This monkey is transparent, slightly greenish-yellow, and changes over several months under water cutoff. After being applied onto a glass plate, it hardens into a transparent film. Example 3 18.5 tons of activated carbon are suspended in 450 tons of ethyl acetate.

The suspension thus obtained was first mixed with di-butyltin dilaurate for 1 hour and then toluylene diisocyanate for 1 hour.
A 75% solution of the product from 1,1-trimethylolpropane in ethyl acetate was added for 1000.5 hours, then di-n-butyl ether. 5 and finally dimethylpolysiloxane having one Si-bonded hydroxyl group in each end unit and an average of about 13 silicon atoms per molecule. The mixture thus obtained was heated under reflux for 1
Heat to boiling for an hour. After cooling the mixture to 50 qO, it is filtered with exclusion of water. The liquor thus obtained has the same properties as the liquor obtained by the method according to Example 2. Comparative Experiment a A mixture of 5 ml of ethyl acetate and 10 ml of a 75% solution of the reaction product consisting of toluylene diisocyanate and 1,1,1-trimethylpropane in ethyl acetate was injected with one Sj- in each terminal unit. Add 0.38 g of dimethylpolysiloxane having bound hydroxyl groups and an average of about 1 silicon atom per molecule.

Since the organopolysiloxane is not soluble in the other mixture components, the mixture thus obtained is cloudy;
It remains unchanged for several days under water cutoff. After application to a glass plate, the mixture hardens to form a cloudy coating. Comparative Example b Tolylene diisocyanate in ethyl acetate and 1.1.
A 75% solution of the reaction product from 1-trimethylpropane (heated to 75° C. with exclusion of water) has an average of 1 Si-bonded hydroxyl group in each terminal unit per molecule at 29.2%. Then, approximately 200 g of dimethylpolysiloxane having silicon atoms is added dropwise.

The mixture thus obtained is heated to boiling under reflux for 2 hours. A colorless powdery precipitate is obtained in which no organopolysiloxane can be detected. The viscosity of the organopolysiloxane solution on this precipitate increased relative to the viscosity of the organopolysiloxane solution used. Example 4 0.1 tsp of di-butyltin dilaurate was added to the mixture whose preparation was described in Comparative Example a, and the mixture was allowed to stand at room temperature for 1 hour while shutting off water.

An almost clear solution is obtained, from which the sample hardens on the glass plate to form a slightly cloudy film. This solution becomes jelly-like after a few days. Example 5 Approximately 80% of 2,4-toluylene diisocyanate and 200% dimethylborisiloxane having one Si-bonded hydroxyl group in each terminal unit and having an average of about 1,000 silicon atoms per molecule; 11.76 mixture of about 20% 2,6-toluylene diisocyanate,
Add 200 parts of toluene and 0.29 parts of di-n-butyltin dilaurate.

Claims (1)

Claims: 1. A unique reaction with an organopolysiloxane having at least one Si-bonded hydroxyl group to produce an organopolysiloxane having a substituted carbamoyloxy group bonded to silicon via oxygen. A method for producing an organopolysiloxane, which comprises reacting at least one monovalent or polyvalent organic isocyanate as a component in the presence of an organotin compound. 2. The process according to claim 1, wherein the organopolysiloxane having at least one Si-bonded hydroxyl group is a diorganopolysiloxane having in each end unit one Si-bonded hydroxyl group. . 3. In the reaction of organopolysiloxanes having at least one Si-bonded hydroxyl group with organic isocyanates, at least one solid organotin compound is used and for the removal of this catalyst under exclusion of water. 3. The method according to claim 1 or 2, wherein the reaction product is filtered. 4. The method according to claim 3, wherein activated carbon is used as the solid carrier.