DE1795565A1 - Process for the preparation of linear polymeric polydiorganosiloxanes which carry organophosphorus side groups - Google Patents

Description

Process for the production of linear polymer polydiorganosiloxanes, which carry organophosphorus side groups.

It is known to use razor blades to improve shaving properties to be provided with a coating made, for example, of polytetrafluoroethylene and cross-linked Polysiloxane consists.

Leave the polytetrafluoroethylene producing the desired effect can only be achieved through complex and expensive processes at high temperatures under pure nitrogen or apply a bad atmosphere to chrome steel blades. By the proportionate high temperature stress on blades treated with polytetrafluoroethylene a drop in hardness cannot be avoided.

Polysiloxanes must be carefully maintained by temperatures and Times on the blades are networked, which requires a greater amount of equipment.

With the invention, a new class of substances has been found which surprisingly apply to blades of all kinds at room temperature and gives the blades excellent shaving properties over a longer period of time. Here it is not necessary to fix the substance on the To network blades, as is the case with previously known substances. It can however, in certain cases, elevated temperatures of up to 2000C can also be used. Above all, the substances can also be used on normal carbon steel blades raise.

The substances used according to the invention are organophosphorus-substituted polydiorganosiloxanes with varying levels of P (0) (0H) 2 groups in the side chain with the following general structure: In this formula: R1, R2, R3 = alkyl, aralkyl, alkaryl or aryl, preferably methyl and / or phenyl Z = unbranched or branched hydrocarbon radical, preferably -CH2, CH2-, - (CH2) 3 -, - CH2-CH -CHS - CH2-CH (CH3) # CH2, - CH2-CH C (CH3) 2 -µ = 0 to 500 x = 1 to 10 000 With a high content of P (0) (0H) groups, the product is a viscous rubber and becomes softer as the content of P (O) (OH) 2 groups decreases, to ultimately form a highly viscous oil. The products are easily soluble in numerous organic solvents and can be sprayed in solution onto cold or warm razor blades. Additional silicone oils and paraffin oils of various viscosities or octovmethylcyclotetrasiloxane, inter alia, in contents of 5-300%, based on the solid product, can preferably be added to the solution. The coating can be heated for a few seconds to hours at room temperature or, depending on the composition, at temperatures up to 2000C. He is not networked. It is believed that the P (O) (OH) 2 groups cause adhesion to the steel surface. After drying, the coating can optionally be sprayed over with silicone oils of various viscosities, with octamethylcyclotetrasiloxane or with paraffin oils. It is effective over a large number of shaves and hydrolytically insensitive, which is a particular advantage, since the desired shaving effect is retained even after immersion in hot water. Even wiping the blades with a cloth does not impair the desired effect.

The coating of the blades changes with longer storage and with higher temperatures do not.

The products according to the invention are obtained by adding dialkyl phosphinate, preferably the diethyl ester (C2H5O) 2P (0) H, (II), or compounds of the (RO) 2P (S) H type to regular or random alkenyl groups, preferably vinyl - or allyl or methallyl groups containing polydiorganosiloxanes of various molecular weights with the general formula: R1, R2, R3 obtained as in formula (1) β-O to 500 X = 1-10,000 Y = monounsaturated branched or unbranched hydrocarbon and subsequent saponification of the reaction products.

The products to be used according to the process are firm to soft Low to very high molecular weight substances soluble in numerous solvents. The compounds described are obtained in high yields. The regular Compounds according to the general formula (III) are by polycondensation of «« -Polydiorgano-silo xanediols with vinyl (or allyl or meta .llyl) methyldichlorosilane obtained in the presence of HCl acceptors. The addition from (II) to (III) can either be at low temperatures of -200C to + 20 ° C in the presence a solubilizer, e.g.

Diisopropyl ether can be made by UV irradiation, or by heating to 60-180 ° C in a suitable solvent in the presence of azodiisobutyronitrile or other radical generators. The reactions are preferably carried out in a nitrogen atmosphere carried out. It is also advantageous to use (II) in excess, if necessary, to suppress the homopolymerization tendency of (III). In the reaction can (II) partially incorporated into the polysiloxane chain, with Si-O-P bonds develop. However, these are split up again in the subsequent hydrolysis, whereby the polysiloxane chain is regressed.

The hydrolysis of the P (0C2H5) 2 groups is best carried out for several hours Heating a solution with aqueous concentrated mineral acids or other strong ones Acids for reflux. DigLyme or toluene can be used as solvents, Aqueous hydrochloric acid concentrated as an acid.

The solutions of the products are then washed free of halogen ions, and the solvent is evaporated in vacuo to 0.5 torr and temperatures up to 1500C. The solid residue is soluble in numerous organic solvents, such as e.g. in methyl isobutyl ketone, in acetone and carbon tetrachloride. In these solvents dissolved, the substance is sprayed onto the blades or u- by dipping. a. upset, as described in the following examples.

For the production of polydimethylsiloxanes containing P (O) (OH) 2 groups the following examples are given: Example 1 9.12 £ t of a real Polydimethylsiloxane with a content of 1 vinyl group per 7 Si atoms and 27.6 o Phosphinic acid diethyl ether (PDE) are dissolved in 30 ccm of diisopropyl ether, 0.1 g of azodiisobutyronitrile (AIBN) were added and under a nitrogen atmosphere for 70 hours refluxed. After that, the solvent and excess PDE are vacuumed distilled off and the residue heated to 1200C for three minutes under 0.5 mm Hg. 10.2 g of a viscous, colorless oil are obtained.

This oil is dissolved in 40 cc diglyme, 20 cc more concentrated with stirring Hydrochloric acid was added and the mixture was refluxed for fourteen hours. After cooling down 10 ccm of ether are added with further stirring and then 40 ccm of water. The organic layer is separated from the aqueous phase and the latter three times shaken out with 15 ccm of ether each. The united ethereal solutions become then washed twice with 20 ccm of water each time (C1-free) and the ether is distilled off. The residue is heated to 1254C at 0.5 mm Hg for 3 minutes. It will be 7.5 g of a rubber obtained.

Example 2 9.78 of a polydimethylsiloxane random with a Content of 1 vinyl group per 13 Si atoms and 13.8 g of PDE are in 20 g of diisopropyl ether dissolved and added 0.1 g of AIBN. The procedure of Example 1 is then continued. It 8 g of a rubber are obtained which is softer in consistency than that obtained according to Example 1.

Example 3 10 g of a random polydimethylsiloxane with a The content of 1 vinyl group per 25 Si atoms and 2 g of PDE is found in 32 g of diisopropyl ether dissolved and added 0.1 g of AIBN. The procedure of Example 1 is then continued. It 7 g of a very highly viscous, barely flowable oil are obtained.

Example 4 2.35 g of a regular polydimethylsiloxane with a The content of 1 vinyl group per 7 Si atoms and 6.4 g of PDE is found in 8.1 g of diisopropyl ether dissolved and the mixture in a quartz vessel under a nitrogen atmosphere for 100 hours irradiated with UV light. The vessel is cooled to about 20 ° C. by water held. The product is then further processed as indicated in Example 1. 2 g of a rubber-like substance are formed.

Example 5 According to Example 1, an adduct is produced which but not in diglyme, but saponified as follows: 0.8 g of the adduct are Dissolved in 40 cc of toluene and added 20 com of concentrated hydrochloric acid. After that, will heated under reflux for sixteen hours with stirring. The organic phase is separated off and washed four times with water.

After distilling off the toluene and briefly heating the residue at 1000 ° C. below two torr, 6 g of a rubbery substance remain.

Example 6 A mixture of 2.82 g vinylmethyldichlorosilane, 30.96 g of dimethyldichlorosilane and 0.2 g of trimethylchlorosilane are added at 20 ° C. with stirring added dropwise to a mixture of 40 g of pyridine and 250 ccm of water. After that, 2 ccm of ether was added and the mixture was stirred at 200C for a further hour. The organic layer is separated off and the aqueous phase is extracted once with ether. The essential Layer is combined with the other organic phase and this solution with water washed and dried over CaCl. After distilling off the solvent and Heating the residue to 1000C under two torr leaves 17.3 g of an oil, that is a random polydimethylsiloxane represents which in Contains an average of 1 vinyl group per 7 Si atoms.

4.89 g of this oil are mixed with 6.9 g of PDE in 10.2 g of diisopropyl ether dissolved and 0D6 g of AIBN added. It will be eighty hours under a nitrogen atmosphere heated to reflux, after the first twenty-four hours an additional 0.06 g AIBN can be added. After distilling off the solvent and the excess PDE, the residue is heated briefly to 100 ° C. under 0.5 torr. It will be used as a Residue obtained 5.2 g of the oily adduct.

4.8 g of this adduct are dissolved in 20 ccm diglyme and taken under 10 cc of concentrated hydrochloric acid are added while stirring; fourteen hours becomes reflux heated. After diluting with water, the organic phase is washed three times with ether extracted.

The combined organic solutions are then washed twice with water washed and dried over CaC12. After the solvent has been distilled off the residue is briefly heated to 1200C under 0.5 Torr.

3.2 g of a rubber-like mass remain.

Claims (3)

Claims 1. Process for the production of linear polymers Polydiorganosiloxanes which carry organophosphorus side groups, characterized in that that an addition of the phosphorus compounds to the unsaturated polysiloxanes in The presence of solvents is carried out by heating to temperatures of 40 - 180 ° C. 2. The method according to claim 1, characterized in that the addition carried out in the presence of radical-forming substances such as azodiisobutyronitrile will. 3. Process for the production of linear polymeric polydiorganosiloxanes, which carry organophosphorus side groups, characterized in that an addition of phosphorus compounds at temperatures from 2000 to 1000C under UV radiation in a nitrogen atmosphere and using a molar excess of phosphorus compounds he follows.