DD255737A1 - METHOD FOR PRODUCING SILOXYL SALKENDIYL-BIS-OMEGA HYDROXYPOLYOXYALKYLENEES - Google Patents

Abstract

The invention relates to the preparation of siloxanylalkendiyl-bis-o-hydroxypolyoxyalkylenes which are useful as precursors for surfactant synthesis, as surfactants, but also as intermediates for organic synthesis. The siloxanylalkendiyl-bis-io-hydroxypolyoxyalkylenes of the general formula I, where R, = organosilyl, organosiloxanyl, polyorganosiloxanyl radicals R, = hydrogen or short-chain alkyl radicals R, = CH, -CH, -O-CHCH, -CH, groups χ = 1 to 50 X "X

Description

2 2

^RR with

R ¹ = organosilyl, organosiloxanyl, polyorganosiloxanyl radicals R ² = hydrogen or short-chain alkyl radicals R ³ = CH ₂ -CH ₂ - or -CHCHa-CHa groups χ = 1 to 50, characterized in that alkynediols of the general formula II,

HO-CRi-C = C-CRi-OH; Il

wherein R ^{2 has the} abovementioned meaning, with addition of 0.05 to 5 wt .-% of an electrophilic catalyst in a molar ratio of 1: 2 to 1: 100 with alkylene oxide by intensive mixing at a reaction temperature of less than 100 ⁰ C, preferably at 50 ° C to 90 ⁰ C, under atmospheric pressure and inert gas atmosphere to Alkindiyl-bis - &> - hydroxypolyoxyalkylenen IH

2 2

R ^ R

C-V-0 (R ³ O) H

Ht 3 "'

CC- 0 (R- ⁵ O) H

2 2

R ^ R

reacted and this, optionally with blocking of the terminal OH groups and / or addition of an inert solvent for homogenization of the reaction mixture, in the presence of a hydrosilylierungskatalysators in amounts of less than 10 "" ² mol / mol triple bond at 50 ° C to 150 ⁰ C, preferably at 100 ⁰ C to 120 ° C, in a molar ratio of 1: 1 to 1: 1.3 with H-siloxanes HR ^{1 are} completely reacted within 1 to 7 hours.

Field of application of the invention

The invention relates to a process for the preparation of siloxanylalkendiyl-bis-tu-hydroxypolyoxyalkylenes which can be used as precursors for surfactant synthesis, as a surfactant and as intermediates for organic synthesis in general.

Characteristic of the known state of the art

A specific method for the preparation of siloxanylalkendiyl-bis-oj-hydroxypolyoxyalkylenes has hitherto not been described in the patent literature.

Comparable methods are syntheses for preparing siloxane polyoxyalkylene block polymers. Starting materials here are allyl alcohol, alkylene oxides and H-siloxanes. Disadvantage of this method is working under pressure. Another disadvantage of such methods is the implementation of the reaction in excess of the polyether component (DE-AS 1220615, GB 1 376920, DE-OS 2207607, DE-OS 1745356, DE-OS 1745522, DE-AS 1745355, GB-PS 1195235, GBPS 1 341 028, GB-PS 1 220741, US-PS 3564037) or excess of the H-siloxane component (DE-AS 1493380, GB-PS 1 353743). In this case, separation of the unreacted starting compounds is difficult or practically impossible at all, whereby the utility of the reaction products is significantly reduced. In many cases, the production processes described above for α-alkyl-ω-hydroxypolyoxyalkylene are not only characterized by complicated purification processes, but are additionally bound to expensive, complicated pressure equipment. This is also true for the alkoxylation of alkinols according to GB-PS 864 287, DE-AS 2,036,278, DE-AS 2,241,155, DE-AS 2,241,156, DE-AS 2,241,157 and US Patent No. 3,293,191, the pressures of 5bis20atm and temperatures of 50 ⁰ C to 200 ⁰ C is carried out in an autoclave. Due to the exothermic reaction under these reaction conditions, the dosage of the alkylene oxides

especially difficult. An additional disadvantage of these processes is the formation of undesirable polyglycols and the presence of residual amounts of starting alkynols. These processes provide addition products having only 1 to 2 alkylene oxide groups.

Object of the invention

The object of the invention is to produce siloxanylalkendiyl-bis-oy-hydroxypolyoxyalkylenes with as little equipment as possible with high yield and purity.

Explanation of the essence of the invention

The object of the object is to develop a process which allows the preparation of the siloxanylalkendiyl-bis-ω-hydroxypolyoxyalkylenes at atmospheric pressure and low reaction temperatures. Siloxanylalkendiyl-bis-to-hydroxypolyoxyalkylenes of the general formula I.

2 2

R ¹ - C - C - O (R ³ OVH

* I

¹¹ 3

H -CC-0 (R ⁰ O) _x H

Z ^ 2

R * R ^

R '= Organosilyl, Organosiloxanyl, Polyorganosiloxanylreste

R ² = hydrogen or short-chain alkyl radicals

R ³ = -CH ₂ -CH ₂ - or -CHCHj-CHr groups

are prepared according to the invention by alkynediols of the general formula II

HO-CRi-CsC-CRI-OH II

with the addition of 0.05 to 5Ma .-% of an electrophilic catalyst in a molar ratio of 1: 1 to 1: 100 with alkylene oxide by intensive mixing under inert gas atmosphere at atmospheric pressure and a reaction temperature of less than 100 ⁰ C, preferably 50 ⁰ C to 90 ⁰ C. alkinediyl-to-co-hydroxypolyoxyalkylenen

2 2

</ 3

C-C-O (R O) H

fll _ "'"

C-C-O (R O) H

RR. ·.

reacted and these, optionally with blocking of the terminal OH groups with SiIyIgruppen and / or addition of an inert solvent for homogenization of the reaction mixture, in the presence of a hydrosilylation catalyst in amounts of less than 10 " ² mol / mol triple bond at 50 ° C to 150 ° C, preferably at 100 ⁰ C to 120 ⁰ C, in the molar ratio of 1: 1 to 1: 1.3 are completely reacted with H-siloxanes within 1 to 7 hours.

The preparation according to the invention of the siloxanylalkendiylbis-w-hydroxypolyoxyalkylenes can be carried out in a simple apparatus under an inert gas atmosphere and proceeds as a multistage one-pot process.

The reaction of the alkynediols with alkylene oxides is carried out with the aid of electrophilic catalysts, of which in particular tertiary oxonium salts or carbenium salts are suitable.

The alkynediyl-bis-co-hydroxy-polyoxyalkylenes obtained in this way are subsequently reacted with the H-siloxanes, it being expedient if appropriate to block the terminal hydroxyl groups in advance by silylation. The silylation is advantageously carried out by reaction with trialkylhalosilanes in the presence of proton scavengers, such as pyridine or trialkylamine, or with silazanes, preferably with hexamethyldisilazane, in a molar ratio of 1: 1 to 1: 3 at temperatures from 2O ⁰ C to 7O ⁰ C.

For the reaction of the alkynediyl-bis-cu-hydroxy- or alkinediyl-bis-aHrialkylsilyl-polyoxy-alkylenes with H-siloxanes the reaction mixture as hydrosilylation, for example, an organic peroxide, a Ziegler-Natta system or a transition metal compound, preferably Hexachloroplatinsäure, with a Concentration of less than 10 ~ ² mol / mol triple bond, added.

For homogenization of the reaction mixture, it may be advantageous to work in an inert solvent. The optionally blocked with silyl OH groups are released by treatment with water or water-alcohol mixtures at temperatures of 50 ° C to 80 ⁰ C.

-3- Übb

The process according to the invention is characterized by a selective course of the reaction. The resulting double bond is not attacked in the hydrosilylation reaction, so that no unwanted by-products are formed. The process according to the invention makes it possible to obtain pure organosiloxanylalkendiyl-bis-w-hydroxypolyoxyalkylenes in high yield, without the need for complicated separation operations to isolate the reaction product. Also advantageous are the low reaction temperatures and the reaction in normal pressure apparatus.

embodiments

example 1

In a three-necked flask equipped with stirrer, thermometer, gas inlet device and reflux condenser, 86 g (1 mol) of but-2-yne-1,4-diol and 0.43 g (0.5 Ma .-%) Triphenylmethy! Tetrafluoroborat under inert gas atmosphere given. After heating at 70 ⁰ C. 440g initiates (10 mol) of ethylene oxide. The rate of introduction is determined by the complete uptake into the reaction mixture. After about 8 hours the reaction is over.

Then added dropwise at 50 ⁰ C 161 g {1 mol) of hexamethyldisilazane so that the temperature does not rise above 60 ⁰ C. The resulting ammonia is removed by introducing inert gas. To complete the reaction, it is stirred for 5 hours. When the ammonia has been completely driven off, the resulting silyl ether is dissolved in 500 ml toluene, heated to 110 ° C., and 0.5 ml of a 0.1 molar solution of hexachloroplatinic acid in isopropanol is added.

222 g (1 mol) of heptamethyltrisiloxane are added to the mixture so that the temperature does not exceed 120 ° C. After 5 hours, the product is hydrolyzed with 10 ml of water and 18 ml of methanol at 70 ° C to 8O ⁰ C, after completion of the reaction, the volatile constituents in a water jet vacuum and receives 682 ga, "'[2- (1,1,1 , 3,5,5,5-heptamethyltrisiloxane-3-yl) but-2-en-1,4-diyl] bis [ct) -hydrpxypenta (oxyethylene)].

Yield: 99.2% of the theory

¹³ C NMR: 6 _CH : 140.6 ppm Scsl x 138.6 ppm

Example 2

In an Example 1 experimental setup 86g (1 mol) of but-2-en-1,4-diol with 1.03g (1.2Ma .-%) Cycloheptatrienyltetrafluoroborat and 880g (20 mol) of ethylene oxide at 60 to 80 ⁰ C in Ethoxylated for 14 hours. The ethoxylate is suspended in 500 ml of toluene and treated with 0.7 ml of a 0.1 molar solution of hexachloroplatinic acid in iso-propanol and 222 g (1 mol) of heptamethyltrisiloxane so that the temperature does not exceed 120 ⁰ C. After 10 hours, 1,164 g of Q ', a' [2 (1,1,1,3,5,5,5-heptamethyltrisiloxane-3-yl) but-2-ene-1,4-diyl] to ^ -hydroxydeca are obtained (oxyethylene)]. Yield: 98% of theory

¹³ C-NMR: 8cH = 141.4ppm Scsi = 139.1ppm

Example 3

In an Example 2 analogous setup, 86 g (1 mol) of but-2-yn-1,4-diol are ethoxylated with 5.24 g (4.5 mol%) of cycloheptatrienyl tetrafluoroborate and 1760 g (40 mol) of ethylene oxide. After addition of 1 ml of the described catalyst solution is mixed at 120 ° C with 500 g of a methyl-H-polysiloxane with 0.2% SiH content. An α, α '(2-polysiloxanyl-but-2-en-1,4-diyl) bis [o-hydroxypoly (oxyethylene)] is obtained with an average of 20 ethylene oxide units on each OH group.

Yield: 99.7% of theory.

¹³ C-NMR: Sch = 141.3 ppm Scsi = 139.0 ppm

Claims (1)

Process for the preparation of siloxanylalkendiyl-bis-oi-hydroxypolyoxyalkylenes of the general formula I 2 2 R ^ -C-C-O (R ° O) H ¹¹ 3 H - C - C - O (R ⁰ O) H