SU910640A1 - Bis-[methyladamantylalkyl(aryl)!-disiloxanes for producing polyurethane compositioons - Google Patents

Description

This invention relates to the chemistry of organosilicon compounds, namely, to new bis-methyladamantylalkyl () disiloxanes with the formula VH H Z-Si-O-iSi-Z CH 3 CH 3 CH gOHOH Z Z CHCH to obtain polyurethane compositions. It is known to use bis methylalkyl for the production of polyurethane com positions. GI disiloxanes. However, these compounds contain in the molecule a siloxane bond with alkylene substituents at silicon atoms and, when used for the preparation of polyurethanes, do not provide sufficient tensile strength and heat resistance. The closest to the proposed Compound 1 (of formula I is bis methylfensh1) is a disiloxane of the formula n uu-f-o-f-y) (10 hours cfd) This compound contains a phenyl radical on silicon atoms, which allows to increase the heat resistance of polyurethane composites also slightly increase their strength when stretched. However, the chemical resistance of these by: Shuretan6B is insufficient for their application in acidic and alkaline environments. The aim of the invention is to increase the chemical resistance of polyurethane compositions. or Saryl) 1 -disiloxanes of the formula D, which, when used for the preparation of polyurethane compositions, improve the chemical resistance of 39 of these compositions in comparison with the known bis (methylphenyl; dismoloxanes of the fopmula I) in the same areas. hydrolysis of methyladamantylalkyl (aryl) chloro-hydridesilanes at 92 ° C in toluene in the presence of a catalyst of sulfuric acid ... Example 1. Bis methyl (P-ada mantil-p) -phenyl il) 3 disiloxane. In a three-neck reactor equipped with a stirrer, back cold With a thermometer and thermometer, a solution of 10 g (.0.0314 mol) of methyl (p-adamantyl-b-phenylethyl) chlorohydride-silane in 20 ml of toluene is added, to which 30 ml of 4.2 Z-Horo Sulfuric Acid is added. Thereafter, the reaction vessel is kept under continuous stirring at a temperature of 6 hours. Then the organic layer is separated from the inorganic layer, washed with distilled water until neutral, and the solvent is distilled off. As a result of vacuum distillation in the presence of 1–2 drops of sulfuric acid, 7, 15 Bis Me of tylp-adamantyl- (L-phenyl ethyl) disiloxane, i.e. b.p. 312-315 ° C. 1-1.5 m Hg. Example 2. Bis (methyl-10 mantil) disiloxane. In the reactor of Example 1, a solution of 10 g of 0.0414 mol of methyl-adamantylethyl) chlorohydrideilane is prepared in 20 ml of toluene, to which 30 ml of a 4.2% sulfuric acid solution are added. Further, as in Example 1. 7.38 g (83%) of bis (methyl- | L-adamantylethyl) disiloxane were isolated, b.p. 233-240 ° C / 2 mmHg Example 3. Bis (methyl-15-adamantylbenzyl) disiloxane. In the reactor of Example 1, a solution of 10 g (0.0328 mol) of methyl (G1 – adamantylbenzyl) chlorohydridel in 20 ml of toluene is prepared, to which 30 ml of 4 2% sulfuric acid are added. Further, as in Example 1. 7.85 g (86%) of bis (methyl-α-adamantylbenzyl) disiloxane was ignited, b.p. 310-312С / 2 mm Hg. The physicochemical properties and the PMR data of these compounds are given in Table. 1 and 2. 4 Synthesized bis methyl (adamantylamine aryl) disiloxanes of formula I are tested to make polyurethane compositions. The results of the comparison of the properties of polyurethane; The elastomers obtained on the basis of the known bis-methylalkyl (. aryl) dis-oceananes and the newly synthesized bis t-methyladamantylalkyl (aryl) di-siloxanes are listed in Table 3 The temperatures of onset of decomposition, thermal-oxidative degradation, softening, flowability, tensile strength and chemical resistance of known and proposed polyurethane elastomers were determined under the same conditions. Example 4. Preparation of a bis-based polyurethane composition. methyl l-adam "thyl-5-phenylethylsdisiloxane. In a three-neck reactor, equipped with a stirrer, a reflux condenser with a calcium chloride tube and a thermometer, 1.67 g (0.0028 mol) of bis methyl (tl-adamantine-siloxane) siloxane dissolved in 20 ml of toluene are introduced. 0.50 g LO, 0086 mol) of allyl alcohol and 0.05 g (2.4 wt.% GY, 1N solution of platinum hydrochloric acid in isopropyl alcohol. The resulting mixture is kept under continuous stirring and at a temperature of 75-80 ° C for 7 h The solvent and excess allyl alcohol are distilled. After cleaning with activated carbon in diethyl alcohol and subsequent evacuation for 2 hours at a residual pressure of 1-2 mm Hg at 50-60 ° C, 1.3957 g (70%) is obtained bis methyl (p-adamantyl-ft-phenylethyl) -y-oxo-propyl} disiloxane. 1.3957 (0.0026 mol) of the resulting bis methyl- (p-ad mantil-j-phenylethyl) -jf-hydroxypropyl) disiloxane- is placed in a three-neck reactor equipped with a messenger and a thermometer, and 4.9296 g (0.0026 mol) of polytetramethylene ether glycol is added to it. The mixture is heated to 90-100 ° C with stirring and purging with dried argon and vacuuming it at a residual pressure of 3 mm Hg. within 2 hours. After this, the reaction mass is slowly cooled to 50 ° C and 1.401 g of 0.0057 mol) of 4,4-diphenylmethane diisocyanate and 0.01 ml of tin dibutyldidurinate as a catalyst are added, mixed and evacuated in the indicated

above conditions 5-6 min. The resulting mixture is poured into pre-heated to steel slotted forms, the walls of which are covered with a film of isobutylene rubber. Curing of nomf-5 dimensional films is carried out in a thermostatic cabinet at 50 ° C for 24 hours, followed by raising the temperature to 80-100 seconds and thermostating for 3 days.

Polyurethane compositions based on bis-Ji-adamantylethyl J disiloxane and bis (methyl-ti h / adamantylbenesh1) dis1oxane are prepared according to a similar procedure.

The presence in the macromolecule of polyurethanes of both adamantylenic and aromatic fragments improves the properties of the latter by increasing their chemical resistance by 2-4 times, the temperature of the onset of thermo-oxidative degradation by 30-140 s, softening temperature from 10-18 to 40-42c, flow temperature by 45 -55C with an increase in strength of 1.5-2 times and a decrease in residual deformation to 1.72, 0%.

eleven

910640

12 Table)

Decomposition start temperature, С

TeMnetsaTypa thermo-oxidative deformula of the invention Bis methyladamantylalkyl aryl disiloxane of the general formula. H H 1g I Z-i-0-Si-X-sjJ CHi CHL g-CH2CH2, (O) -CHN pi mi ± 7,

240

225 to form polyurethane compositions. Sources of information taken into account in the examination of j Smetankina N.P. and others. Carbofunctional organosilicon compounds. 1.Difunctional bis (alkylmethylphenyl) disiloxanes - JOH,: 37.1, p.271.

Claims (1)

Claim Bis [methyladamantylalkyl (aryl)] siloxanes of the general formula AND I dais to obtain polyurethane compositions. Z-CH ₂ CH _2> ! CH ₂ CH _2r ίθ