DE1495437A1 - Process for the production of new organosilicon compounds - Google Patents

Description

Process for the production of new Organ @ -silicon compounds Es it is known that organosilicon compounds are used as Gie # and Laocarse Can. Only polysiloxanes come into consideration, however, as a result of inadequate Elasticity, adhesive strength, condensation speed, etc. are only limited Find use as paint resins, and on the other hand, modified silicone resins. Within Of this group, the organosilicon epoxy compounds represent a special one interesting series, as they can be used both as casting resins and as coating resins let use. While such compounds have excellent properties as casting resins have, they have not yet become generally accepted in the paint sector, primarily, because due to the low condensation rate during the baking process the stability of such films, especially when painting shaped objects, is too small. Resins are used to circumvent this disadvantage condensed with excessive hardening agents, there is a risk that the shelf life of a paint made from it is too low due to the progressive condensation is.

According to the invention, the new substances are obtained because organ-silicon compounds which contain at least two H-Si groups with mono- and / or polyunsaturated Mono and / or polydioxolanes, if appropriate in the presence of catalysts, such as Platinum, platinum compounds, organic peroxides and / odex UV rays implemented will. Preferably only 5-50 g of the H-si groups with the unsaturated reacted dioxolanes.

The reaction takes place at temperatures between 20 and 110 ° C within from 30-60 minutes, optionally in the presence of solvents. The remaining H groups are then in a known manner with unsaturated epoxy groups containing compounds implemented.

In certain cases it is useful to change the order of implementation the organosilicon compounds with the unsaturated Diexolannen and the unsaturated ones Reverse epoxy compounds. The silicon-containing organic compounds can Be silanes, siloxanes and alkoxysilanes, with at least 2 H-Si groups in the molecule must be included.

The dioxolanes preferably belong to the following types of boron or their polymers: where in the formulas 1 and II R un 'are hydrogen and / or radicals of the aliphatic, oyoloaliphatic, aromatic and heterocyclic series and R''are divalent hydrocarbon radicals of these series or substituted bests of these series. In formula III, R and R 'denote divalent hydrocarbon radicals having one to three carbon atoms. In addition, it is also possible to use unsaturated dioxolanes which are obtained by reacting unsaturated aldehydes or ketones with dihydric and polyhydric alcohols.

Polymeric dioxolanes are used twice in dissolved form brought, it is both possible to use the polymeric Dierdhne in a suitable Dissolving solvents as well as polymerization in the presence of a solvent to undertake.

Are substances used in the polymerization that contain active hydrogen atoms? contain, e.g. mono- or polyhydric alcohols, mono- and / or polyhydric silanols, Amines or cyclohexanone are found when di- and polyunsaturates are used Diexolanes at the same time have polyether-diexolanes, which are still reactive double bonds and also react with the organosilicon compounds mentioned can.

The unsettled epoxy compounds can have any character; mono- and / or polyunsaturated mono- and polyepoxy ethers are preferred applied.

Particular advantages of the method according to the invention are to be cited, that by varying the diexelan component, the reactive solvent, of the unsaturated epoxy ether used and the organosilicon compounds As far as possible influencing the physical and chemical characteristics of the same Products is possible, there is a further possibility of variation insofar as d due to the known ring splitting tendencies of Diexlane su linear polyethers under the action of cationic catalysis the oh, §mi'-N, @ h and physical Particularly adhesive varnishes can be influenced.

The products obtained can be made high-temperature-resistant by known processes and hydrolysis-resistant paint resins with extremely good mechanical and electrical properties Process properties whose long-term heat resistance is generally between 160-170 ° C, but when using special hardeners (e.g. Mllitic anhydride) to approx.

18000 can be increased. The burn-in times are approx. 60-90 Minutes at temperatures of 170-200 ° C.

Even with pigment contents of up to 40 *, the films are still pronounced hydrophobic properties strong gloss and plasticity. The stability, elasticity and flowability can be determined by varying the content of epoxy groups Best, dioxolane residues etc. adjust light to the desired level.

The new compounds prepared according to the invention are also suitable as coating resins also as casting resins and adhesives.

Example 1 Tetraphenyl-tetramethyl-tetrasiloxane (2 mol), which by Cohydrolysis of molar amounts of dimethylidchlorosilane and di-phenylmonochlorosilane produced was, is at temperatures between 20 - 110 ° C, preferably between 40-6000, reacted with 1.8 mol of 2-methylene-1,4-dioxaspire- (4,5) -dekan within one hour. Then 2.5 mol of allyl glycidyl ether are added at temperatures between 90 and 15,000, preferably at 110-13,000, in the presence of a diethylene glycol dimethyl ether solution of chloroplatinic acid containing 0.3-0.4% by weight of platinum within a half Added dropwise for an hour. and heated to 150 for another half hour. Afterward becomes the excess allyl glycol ether distilled off in vacuo.

The following compound is obtained in the form of a yellow liquid: The epoxy equivalent is 810; calculated 790. a) 71 g of phthalic anhydride are added to 600 g of the above compound and the mixture is heated to 140-150 ° C for 20 minutes. After decarburization, the clear prepolymer is mixed with 53 g of a 15% 4.4'-diaminodiphenylmethane solution and depending on the usual hardness with 40-90 g of a melamine-formaldehyde condensate and 314 g of cadmium red as pigment, with ethylene glycol to a DIN viscosity of 80-90 sec. Diluted and worked through.

Lacquer bodies are obtained which, after predrying for 30 minutes at 50-60 ° C no longer run off and within 2-1.5 hours at 180-190 ° C a highly elastic film with resistance values of approx. 1014 ohms. cm and one Permanent heat resistance of 160-180 ° C. b) 300 g of the above compound are 0.6-0.7 times the amount required for the epoxy equivalent Amount of phthalic anhydride heated to 140-150 ° C for 20 minutes. To to the Cool down to the above. 300C, 0.7-1.0 ml of oonc. Perchloric acid (70%) added and the batch is heated to 140-1500C for 60 minutes.

Then immediately 23 g of triethanolamine are added. After a A standing time of 15-20 hours is achieved with 25 g of a 10% strength aluminum isopropylate solution in ethyl acetoacetate and heated again to 1400C for 5-10 minutes. To the Pigmentation is done with #thylglycol to 60-70 DIN-sec. diluted and with 31% cadmium red pigment with the addition of 8% melamine-formaldehyde condensate and 5% diaminodiphenylmethane offset.

Example 2 2 moles of tetraphenyl-tetramethyl-tetrasiloxane are mixed with 3.5 mol of allyl glycidyl ether reacted with one another in the manner described in Example 1. The reaction mixture is then treated with a solution of polymeric 2-methylene-1,4-dioxsapire- (4,5) -dekan in toluene, which contains "0.5 mol" of double bonds, at temperatures of 20-1100C, preferably between 40 and 60 ° C., reacted. The reaction product possesses Depending on the degree of polymerization of the dioxolane used, an epoxy equivalent of 500-830.

Example 3 Tetraphenyl-tetramethyl-tetrasilexane (2 mol), which by Cohydrolysis of molar amounts of dimethyldichlorosilane and diphenylmonochlorosilane produced will be at. Temperatures between 20-110 ° C, preferably between 40-6000. with 1.8 mol of a solution polymerization of 2-methylene-1,4-dioxaspireo- (4,5) ~ decane polymer solution obtained in ethylene glycol reacted within one hour. Thereafter, 2.5 mol of allyl glycidyl ether at temperatures between 90 and 150 ° C. are preferred at 110-13000, in the presence of a diethylene glycol dimethyl ether solution of chloroplatinic acid containing 0.3-0.4 weight platinum within half a Added dropwise for an hour and heated to 150 ° C for another half hour. Afterward the excess allyl glycidyl ether is distilled off in vacuo.

Example 4 1 mole of hexaphenyltetrasiloxane obtained by cohydrolysis of 3 moles of diphenylchlorosilane and 1 lol of SiHCl3 was obtained, becomes 3 moles of allyl glycidyl ether, to which a trace of chloroplatinic acid is added, at 110 ° C within 2 hours added dropwise with stirring. The mixture is then stirred at 140 ° C. for a further hour.

Then 1 mol of 2,2-dimethyl-4-methylenedioxolane (1,3) is added dropwise at about 50 ° C. over the course of one hour. Subsequently unreacted allyl glyoid ether and dioxolane are distilled off in a water jet pump vacuum. The following compound is obtained as a reaction product as a yellow-brown, viscous liquid: The fluid has an epoxy equivalent of 374; ber. 361.

Example 5 1 mol of tetraphenyldisiloxane is in the manner described in Examples r and 3 in the presence of chloroplatinic acid with 1 mol of allyl glyde ether and 0.5 X.ol of cycloherxane-bis-1,4- [4-methylenedioxolane (1,3) - ] brought to conversion, the result is a highly viscous yellow-brown liquid of the following compound: and has an epoxy equivalent of 614; ber. 608.

Claims (3)

P a t e n t a n s p r u c h e 1. Method of making nine Organosilicon compounds, characterized in that # organosilicon compounds with at least 2 H-Si groups in the molecule with mono- and / or polyunsaturated Monomo- and / or polydioxolanes at temperatures of 20-110 ° C, if necessary in the presence of catalysts, the amount of unsaturated added Dioxolane is preferably to be chosen so that only -5-50% of the H-Si groups for implementation arrive and the remaining H-si groups with unsaturated ones in a known manner E; containing oxide groups. Connections are implemented. 2. The method according to # claim 1, characterized in that organic silicon epoxy compounds that contain H-Si groups with one or more Mono- and / or poly dioxolanes, which can also be present in dissolved form, optionally in the presence of various catalysts. 3. The method according to claim 1 and 2, characterized in that the used di- and / or polyunsaturated monodioxolanes or during the addition to the siloxane with substances carrying active hydrogen atoms, z, B, mono- and / or polyhydric alcohols, silanols, amines, cyclohexanone, etc., be unset.