CS196941B1 - N-bis/beta-hydroxyethyl/gamma ureidopropyltrialkoxysilanes - Google Patents

Description

MIŠKOLCI ANTON prom. chem., FLOROVIC STANISLAV ing., FORRÓ JURAJ, TRNAVA, MARTINOVIC BOHUMÍR, KATLOVCE and MARTIŠOVIC JOZEF, CLOSE (54) N-bis (beta-hydroxyethyl) gamma ureidopr opyltrialkoxy strong

The present invention relates to novel N‘-bis (beta-hydroxyethyl) gamma ureidopropyltrialkoxysilanes.

The organosilicon derivatives of 2,2'-iminodiethanol have been used in the silicate industry as a coating improving the antistatic properties and reducing the coefficient of friction of the impregnated surface. In the case of the treatment of silicate fibers, the surface treatment must also provide for a number of important processing properties with regard to their application application. These tasks were solved by a film-forming mixture

CH 2 —CHCH ₂ O (CH ₂ ) 5 Si (OC 2 H 5) 3 + HN (CH ₂ CH ₂ OH) 2 substances, lubricants, wetting agents, antistatic agents and binders. For the sake of simplification of these systems, efforts are being made to use lubricating agents which perform multiple functions simultaneously. U.S. Patent 2,946,701 describes the preparation and use of silanes, prepared by the addition of amines to epoxisilanes, as a surface treatment of glass fibers. In this way, it is possible to prepare various adducts based on 2,2'-iminodiethanol, e.g.

- * (HOCH2CH2) 2NCH2—

OH i

—CHCH2O (CH2) 3S1 (OC2H5) 3

While using this adduct for the surface treatment of glass fibers, good antistatic and slip properties of the fibers are achieved, it is insufficient to improve adhesion, especially to epoxy resins. The same is true for trialkoxysilanes, which can be represented by the general formula:

(HOCH 2 CH 2) 2N (CH 2)> _n Si (OR) 3 wherein R is alkyl and an integer of 1 to 6. Some types of these compounds can be prepared according to CS aut. halomethyltrialkoxysilanes in an alkaline medium, preferably in a solution of sodium alcoholate at a temperature of 50 to 150 ° C.

The present invention provides novel N‘-bis (beta-hydroxyethyl) gamma ureidopropyltrialkoxysilanes of the general formula

ABOUT

HOCH 2 CH 2 K II y NCNH (CH 2) 3 Si (OR) 3

H0CH2CH2 ⁷

HN (CH 2 CH 2 OH J 2 + O = C = N (CH 2) 3 S 1 (OR) 3 in which R is methyl or ethyl)

{HOCH2CH2J2NCONH (CH2) 3Si (OR) 3

The choice of suitable solvents is the considerably limited presence of the broadly reactive isocyanate functionality and the polar properties of 2,2'-dimodiethanol. Dioxane may be used as a good solvent in the syntheses of the invention. We have found that the addition is advantageously carried out in the absence of a solvent. The resulting silanes can be used in various applications in the form of solutions in water and in most polar organic solvents. The invention is further illustrated by way of examples.

Example 1

Preparation of Silane of Formula (HOCH2CH2) 2 NCONH (CH2) / 3Si (OCH3) 3

The reaction was carried out in a three-necked flask with an Anschutz flask fitted with a stirrer, an in-line cooler with a drying tube, a contact thermometer, and a separatory funnel.

handle:

31,5 g (0,3 mol) 2,2'-iminodiethanol (without water)

74.2 g (0.3 mol) gamma isocyanatopropyltrimethoxysilane 100 g dioxane (without water).

2,2'-Iminodiethanol was dissolved in dioxane and placed in a flask. Silane was added slowly from the separatory funnel over 1 h and the reaction was allowed to proceed at 80 ° C for 3 h. The solvent was distilled off from the silane in vacuo and the residue was analyzed by paper chromatography. We have found that the conversion of this reaction is practically 96-100%. Elemental analysis for C 11 H 26 O 6 N 2 Si (mol - 310.43) Calculated: 9.02% N, 9.05% Si;

Found: 9.18% N; 9.23% Si;

The resulting silane is a clear, pale yellow liquid and similar to 2,2'-iminodiethanol itself is also viscous.

It is soluble in most polar organic solvents. It forms a slightly cloudy solution in water, which becomes clear after the hydrolysis of the silane. It is preferred to catalyze its hydrolysis by adjusting the aqueous solution to a pH in the range of 3.5 to 5.

Example 2

Preparation of silane of formula (HOCH2CH2 j2 NCONH (CH2 J3S1 (OC2H5 j3))

10.5 g (0.1 mol) of 2,2'-iminodiethanol

26.1 g (0.1 mol) gamma isocyanatopropyltriethoxysilane

The silane is added slowly to the 2,2'-iminodiethanol with stirring so that the temperature of the reaction medium does not exceed 50 ° C. The reaction was complete after stirring for 1.5 h. Yield 33 g, i. 97% of theory. For C12H28O6N2Si (mol. Weight - 324.46)

N, 8.63; 8.66% Si; Found: N, 8.80; 8.72% Si;

Example 3

The silanes were used as a 0.5% aqueous glass fiber treatment solution. Hydrolysis of the silanes was catalyzed by the addition of acetic acid to pH-4. The prepared finishes were applied to the glass fiber directly during its production from a platinum furnace. The 13 µm thick E-glass fibers treated in this way were allowed to dry for about 24 hours and were dried at 125 ° C for 4 hours. Glass strands were used as a reinforcement of epian resin based on diane and epichlorohydrin having an epoxy group content of 0.52 equiv./100g and a viscosity at 25 ° C of 12,330 mPa.s. The resin was cross-linked using diethylenetriamine with an amine number of 1638 mg KOH / g and contained 65% by weight of glass fibers. Evaluation of laminates was carried out by bending strength test according to ČSN 64 0607 and artificial aging by boiling in water for two hours. The results obtained are shown in the table.

Jadhesion promoter R - (CH 2 J 3 - Si (OC 2 H 5) 3

Bending strength (MPa) dry after boiling (HOCH2CH2J2NCONH— 1030 (HOCH2CH2J2N- 970 (HOCH2CH2) 2NCH2CH (OHJCH2O- 982)

Hydrolyzing and condensing the silanes to the corresponding polysiloxanes on the glass surface gives clear films with high adhesion.

980

951

960 greasy feel with excellent sliding properties.

Claims (1)

Subject of the invention: 31 * N ‘-bis (beta-hydroxyethyl) gamma ur e-propyloxytrialkoxysilanes of formula O HOCH2CH2K II> NCNH (CH2) 3 Si (OR) 3 HOCH2CH2 ^Z wherein R is methyl or ethyl.