DD282014A5 - PROCESS FOR PREPARING ORGANOSILYL, ORGANOSILOXANYL, BZW. ORGANOPOLYSILOXYL SUBSTITUTED ALKENOL COMPOUNDS - Google Patents

Abstract

The invention relates to a process for the preparation of organosilyl-, organosiloxanyl- or organopolysiloxanyl-substituted alkenol compounds which are used as surfactants in surfactant blends or as intermediates in organic synthetic chemistry. The compounds are prepared according to the invention by reacting alkyl-substituted alkynols in a reaction step without protecting the OH groups with organosilane, organosiloxane and / or organopolysiloxane compounds in an organic aprotic polar solvent in the presence of a catalyst at temperatures between 20 and 130 ° C. alkenol compound; organosilyl or organosiloxanyl substituted; Alkynols, alkyl-substituted; organosilane; organosiloxane; surfactant synthesis}

Description

R ¹ CsCCR ² R ³ OH II

in which the radicals R ¹ , R ^? and R ^{3 have} the abovementioned meaning, are reacted with organosilane, organosiloxane and / or organopolysiloxane in the equimolar ratio of triple bond and SiH groups in an organic aprotic polar solvent in the presence of a catalyst at temperatures between 20 and 130 ⁰ C. ,

2. The method according to claim 1, characterized in that is preferably used as the organic aprotic polar solvent dioxane.

3. The method according to claim 1, characterized in that the reaction is catalyzed by UV radiation, an organic peroxide or a transition metal compound.

4. Process according to claims 1 and 3, characterized in that preferably hexachloroplatinic acid is used in proportions of 0.0001 to 0.00001 mol / mol triple bond as the catalyst.

5. The method according to claim ^, characterized in that the organosilane, organosiloxane or organopolysiloxane compounds used have 1 to 80SiH groups.

Field of application of the invention

The invention relates to a process for the preparation of organosilyl, organosiloxanyl or organopolysiloxanyl-substituted alkenol compounds. These are both organosiloxanyl-substituted alkenes having one or more hydroxyl groups and / or one or more double bonds in the molecule and also organosiloxanes! Organopolysiloxanes with one or more of the aforementioned alkenyl substituents.

Di-? Compounds according to the invention can be used as surfactants, in mixtures of surfactants or as intermediates in organic sorption chemistry.

Characteristic of the well-known.! State of the art

According to US Pat. No. 2,827,281, silicon-containing alkenols can be prepared by addition of Si-H to acetylenic bonds, with high reaction temperatures and long reaction times being disadvantageous and the course of the reaction being very dependent on the nature of the reactants and the catalyst concentration.

The disadvantages of a further process (DE-OS 2529782) for the preparation of silicon-containing alkenols, the reaction of an acetylenic alcohol with an H-siloxane in the presence of catalytic amounts of a platinum initiator within 16 hours at 70 ° C, are the very low yield (2 to 20 %) and the danger of a spontaneous uncontrollable exothermic reaction. Another method (DE-OS 2554001 (describes the reaction of an acetylenic alcohol and a H-siloxane in the vapor phase at 210 to 45O ⁰ C in the reaction tube in the presence of a platinum catalyst.) However, the high working temperatures leading to decomposition phenomena and the inapplicability have a disadvantageous effect for a large-scale production.

In US-PS 3971818 a method vorgoschlagen, but which is not feasible in the art and is only suitable for the production of very small quantities on a laboratory scale. The reaction mixture of acetylenic alcohol and H-siloxane is passed through at 300 to 400 ° C. and residence times of 1 to 2 seconds through a gas-liquid chromatographic column whose support material is coated with a layer of platinum catalyst The yields are only 30 to 35%. DD-PS 239596 describes a process in which the preparation of siloxanyl-but-2-en-1,4-diol compounds takes place in three steps In the first step, the OH groups of the butynediol are protected by silylation Depending on the type of silylating agent used (trimethylchlorosilane and / or hexamethyldisilazane), additional filtration of the ammonium chloride formed and removal of the solvent used (see Examples 1 to 3) or expulsion of the released ammonia (compare Examples 4 to 5) In the second step, the silylated butynediol with an SiH compound in the presence of a known catalyst at elevated temperature oh ne addition of a solvent hydrostlylated. The exothermic nature of the hydrosilation leads to a significant temperature jump (see Example 1), which makes it difficult to control the reaction in the art and requires additional safety measures. In the third step, the protecting groups are cleaved by alcoholysis / hydrolysis in a several hours consuming reaction. Overall, the process requires a great deal of work, time and material. Expensive aids (eg securing agents ...) can not be returned to the process without additional regeneration stages. However, their use in the process is imperative, which exemplifies Example 11. In this example, butynediol is hydrosilated without prior protection of the OH groups with an H-siloxane. After working up the reaction mixture by distillation, a fraction (62 parts by weight in%) with a GC content of 40% of the target product is obtained. The selectivity of the hydrosilation of butynediol under these conditions is thus only 25%. This result is consistent with statements in the literature. In investigations on the hydrosilation of OH-unprotected alkynols, it has been found that numerous secondary reactions (inter alia dehydrocondensation, rearrangements, etc.) occur (Z.Obsc.Chim.42.1972, p. 1767ff. [CA 78/29888 =>|; ibid., , 5, 1975, pp. 2349ff. [CA 84/31200 d]; ibid 46, 1976, p. 865ff. [CA 84/180365 p); ibid 46,1976, p.2531 ff .; ibid., 48, 1978, pp. 1113ff. [CA 89/109677 q); Soobsc.Akad.NaukGruz.SSR 65.1972, S.73ff. [CA 76/140281 ml; ibid. 79. V · 5, S.89ff. [C /. 83/193462 xj).

The use of solvents (eg, benzene) causes a certain influence on the course of the hydrosilylation without, however, completely excluding dehydrocondensation in the case of secondary and primary alkynols (Z.Vses.Chim.O-va ^ ejdeS.S ^ ISff. [CA 100/174909 b]; Dokl.Akad.Nauk.Az.SSR 41, 1985, p. 50ff. [CA 104/148961 al; lzv.Vysc.Uceb.Zaved.Chim.Chim.Technol. 28, 1985, p.24ff. [CA 106/5127 pl).

In the literature it is argued unanimously that side reactions of the OH groups in hydrosilylation reactions of secondary and primary alkynols are largely ruled out only by silylation of the OH Gruppc ^ (Z.Obsc.Chim.48, 1 ^t J78, S.1113ff. lzv.Akad.NaukGruz.SSR, Ser.Chim.6 [2], 1980, pp. 136ff. [CA 94/15801 b]).

Object of the invention

It is the object of the invention to prepare silyl-, siloxanyl- and polysiloxanyl-modified alkenol compounds by a simplified one-pot process from alkynes having one or more hydroxyl groups and one or more triple bonds in the molecule by reaction with H-silanes, H-siloxanone or H-silanes. Polysiloxanes in high yields, without the use of Dme ;, and at reaction temperatures below 13O ⁰ C to produce.

Explanation of the essence of the invention

The object of the invention is to produce organosilyl- or organosiloxanyl- or organopolysiloxanyl-substituted alkenol compounds according to a uniform, easily carried out one-step process.

The object is achieved in that organosilyl or organosiloxanyl or organopolysiloxanylsubstituierte alkenol compounds of general formula I,

H in the

R '= H, alkylene having 1 to 10 C atoms or methylol residue,

R ² = H, alkyl radical having 1 to 6 C atoms,

R ³ = H, alkyl radical having 1 to 6 C atoms or 3-hydroxypropynyl radical,

X = organosilyl radicals having lower alkyl, alkoxy and / or aryl groups, straight-chain, branched-chain and / or cyclic organosiloxanyl radicals having 1 to 20 Si atoms and lower alkyl, alkoxy and / or aryl groups, is straight-chain and / or branched-chain organopolydiloxanyl radicals having 20 to 700 Si atoms and lower alkyl, alkoxy and / or aryl groups,

be gelled by the present invention in a reaction step without protection of the OH groups dor general formula II, R ¹ C = CCR ² R ³ OH II

in which the radicals R ¹ , R ² and R ^{3 have} the abovementioned meaning, with organosilane, organosiloxane and / or organopolysiloxane in the equimolar ratio of Drebachbiniung and SiH groups in an organic aprotic polar solvent in the presence of a catalyst at Temperatures between 20 and 130 ⁰ C to be implemented.

Preferably, the reaction takes place at the boiling point of the solvent. Suitable solvents in the context of the invention are aprotic, polar solvents, such as dioxane, but also protic, polar compounds whose protic

Group is sterically shielded, for example, tertiary alcohols. f-s can also be used solvent mixtures of the above compounds.

The reaction is catalyzed by UV radiation, organic peroxides or transition metal compounds, especially: hexachloroplatinic acid, in proportions of 0.0001 to 0.00001 mol / mol triple bond.

The process according to the invention leads to the desired organosilyl, organosiloxanyl or organopolysiloxanyl-substituted alkenol compounds by direct reaction of the alkynols with the silane, siloxane or polysiloxane compounds without protection of the OH groups in yields> 90%.

Advantages of the method according to the invention are:

- Working without securing means (waiver of protective groups and inert gas)

- short reaction times

- One-step procedure

- Process well controlled

- Non-occurrence of by-products

- Reaction temperature regulated by solvent use

The application of the method according to the invention to the preparation of silicon-substituted alkene analogues with polyether radicals, carbonyl, amino and mercapto groups is conceivable.

embodiments

example 1

The reaction mixture of 1.88 g (0.0335 mol) propargyl alcohol, 7.45 g (0.0335rr oil) 1,1,1,3,5,5,5-Hoptamethyltrisiloxan, 10ml abs. Dioxane and 0.015 ml M / 10 H ₂ PtCl _e / i-propanol solution (about 0.000045 mol pi / mol triple bond is boiled for 2 hours at reflux (106 to 11O ⁰ C.) The gas chromatographically determined conversion is 98.7% The product consists of 57.7% of 2- and 42.3% of 3-heptamethyl: isiloxanylprop-2-en-1-ol.

²⁹ Si NMR spectrum:

6 (CH ₃ J ₃ SiO- = 6.88 ppm / 7.16 ppm

I. a -34.36 ppm / -35.00 ppm

Example 2

The reaction mixture of 2.3 g (0.0182 mol) of oct-2-yn-1-o !, 4.05 g of 1,1,1,3,5,5-heptamethyltrisiloxane, 10 ml abs. Dioxane and 0.015 ml of M / 10 H ₂ PtCl ₆ / i-propanol solution are boiled for 2 hours at reflux (106 to 110 ° C). The gas chromatographically determined conversion based on oct-2-yn-1 ol is quantitative. The expected isomeric siloxanyloct-2-en-1-ol compounds are formed.

²⁹ Si NMR spectrum:

6Me ₃ SiO- = 8.3-6.4 ppm

6 == SiC = CH- = -34.0 ... -40.0ppm (multiple signals) 'H-NMR spectrum:

OsSiC = CH- = 6,12-6,25ppm

Example 3

The reaction mixture of 21.9 g (0.1333 mol) triethoxysilane, 11.5 g (0.1333 mol) but-2-yne-1,4-diol, 70 ml abs. Dioxane and 0.03 ml M / 10 H ₂ PtCl _e / i-PrOH solution are refluxed for 2 hours. It forms 2- (triethoxysilyl-but-2-en-1,4-diol. The conversion is 95% based on butynediol.

²⁹ Si NMR spectrum:

6 (EtO) ₃ SiC = CH = -59.0 ppm (broad signal) 'H-NMR spectrum:

6sSiC = CH = 6.2-6.3ppm

Example 4

The reaction mixture of 0.29 g (0.00188 mol) of 4-methyl-1,4,7-trihydroxyhepta-2,5-diyne, 0.837 g (0.00376 mol) of 1,1, 3,5,5-heptamethyltrisiloxane, 2ml abs. Dioxane and 0.0005 ml of M / 10 H ₂ PtCl ₆ / i-PrOH solution are refluxed for 2 hours. The expected different isomeric siloxanylalkenol compounds are formed. The Urr rate is quantitative based on the employed 4-methyl '', 4,7-trihydroxyhepta-2,5-diyn.

²⁹ Si NMR spectrum:

6Me ₃ SiO- = 7.93 ppm

-4- 232

OsSiC = CH- = -35.0 ... -39.8ppm (multiple signals) 'H-NMR spectrum:

OsSiC = CH- = 6.05-6.35 ppm Example 5

The homogeneous reaction mixture of 0.38 g (0.0017 mol) of pentadec-6-yn-S-ol, 0.38 g (0.0017 mol) of 1,1,1,3,5,5,5-heptamethyltrisiloxane, 5 ml abs. Dioxane and 0.0005ml M / 10H ₂ PtCl _e / i PrOH solution is refluxed for 2 hours. The expected isomeric siloxanyl pentadecenols are formed. The conversion based on the Peni2dec-6-in-5-ol used is quantitative.

²⁹ Si NMR spectrum:

6Me ₃ SiO- = 6.58 ppm; 8,3ppm

OsSiC = CH- = -34.23 ppm; -34.89 ppm 'H-NMR spectrum:

Ss SiC = CH = 6.12-6.28 ppm Example 6

The reaction mixture of 3.75 g (0.044 mol) of but-2-yne-1,4-diol, 7.6 g of H-siloxane (SiH content = 0.585%, M = 2270 g / mol), 30 ml abs. 1 oluen and 0.03 ml M / 10 HjPtCle / i-PrOH solution is refluxed with stirring for 7 hours (115 ⁰ C). The conversion is 100% (GC). The yield of poly (siloxanylbutendiol) is 40%.

Examples 7 to 14

General experiment

The reaction mixture dried solvent, 2g (0.0232mol) but-2-yn-1,4-diol, 5.2g (0.0232mol) 1,1,1,3,5,5,5-heptamethyltrisiloxane and 0.015ml M / 10H ₂ PtCle / i-PrOH solution (about 0.000045 mol Pt / mol triple bond) is refluxed with stirring. The gas chromatographically determined conversion is 100% based on but-2-yne-1,4-diol.

The information on the type and amount of solvent used, reaction time, reaction temperature and selectivity are in

Table 1 summarized.

The selectivity of the reaction refers to the formed 2- (1,1,1,3,5,5,5-Hr> ptamethyltrisiloxanyl) -but-2-en-1,4-diol.

Tab. 1: Hydrosilation of but-2-yne-1,4-diol with 1,1,1,3,5,5,5-heptamethyltrisiloxane in various solvents

example

Solvent amount (ml)

reaction temperature

Reaction time (hours)

S-.lektivität

7 nitromethane 105 ⁰ C 4h 67 10ml 8th acetonitrile 85 ° C 1h 72 8 ml 9 t-butanol 84 ° C 3h 78 10 ml 10 THF 68 ⁰ C 2.5 h 73 8 ml 11 dioxane 105 ⁰ C 2h 95 10ml 12 toluene 117 ⁰ C 8h 88 10ml 13 Essigester 87 ⁰ C 3h 86% 8 ml 14 Dioxane / toluene 111 ⁰ C 3,5 h 94 5 ml / 5 ml

Examples 15 to 36

The equimolar reaction mixture of but-2-yne-1,4-diol and H-siloxane in the solvent dioxane is refluxed in the presence of 0.000045 mol H ₂ PtCl ₆ / mol triple bond for Vh hours.

The conversion based on but-2-yn-1,4-diol is quantitative. Table 2 summarizes the respective reaction mixtures

cited.

Tab, 2: Hydrosilation of but-2-yne-1,4-diol with various H-siloxanes in dioxane

example amount amount polysiloxane M _w solvent No. Butindiol (G) SiH content (G / mol) amount (G) 11.5 (%) 4510 (Ml) 15 4.0 10.0 0,407 17100 60 16 3.6 6.2 0.421 1130 60 17 3.6 7.7 0.683 2270 60 18 3.9 8.2 0,585 5390 60 19 4.2 7.0 0.592 940C 60 20 3.8 6.9 0,630 17,000 60 21 3.9 18.1 0,665 222.5 ^{+ i} 60 22 7.0 20.2 0.453 4510 50 23 7.0 10.0 0,407 222.5 * ' 50 24 3.85 7.6 0.453 2800 15 25 4.8 7.9 0.75 3100 50 26 2.4 13.2 0.35 17000 15 27 7.0 14.0 0,665 9400 50 28 7.0 15.0 0,630 5390 50 29 7.0 15.0 0.592 2 270 50 30 7.0 3.5 0,585 1600 50 31 3.0 3.34 1,086 3300 20 32 4.8 31.0 1,670 2 270 35 33 15.0 38.0 0,585 8310 120 34 14.0 36.3 0.422 222.5 * ' 100 35 14.0 11.5 0.453 282.6 ** ' 100 36 7.0 38.0 0.713 4070 60 37 7.0 0.210 50

* '1,1,1,3,5,5,5-heptamethyltrisiloxane ¹ *' 1,1,1,3,5,7,7,7-octamethyltetrasiloxane

Examples 38 to 41

The equimolar reaction mixture of propargyl alcohol and H-siloxane (SiH.Dreilachbindung = 1: 1) in a solvent

is in the presence of 0.000045 mol H ₂ PtCle / mol triple bond refluxed 2Ίι hours at reflux.

The conversion based on propargyl alcohol is quantitative. Table 3 summarizes the respective reaction mixtures

listed.

Tab. 3: Hydrosilation of propargyl alcohol with various H-siloxanes in solvents

Ex. Quantity (g) amount polysiloxane mw LM-Volume (ml) No. propargyl (G) SiH content (G / mol) alcohol 13.0 (%) 3250 38 0.6 21.0 0.078 4070 Dioxane (30) 39 2.5 126.0 0.210 4070 Dioxane (60) 40 15.0 10.5 0.210 4070 Dioxane (200) 41 1.3 0.210 Toluene (25)

The silicon NMR spectra indicated the uniformity of the reaction products: ²⁹ Si NMR spectrum: 6Me ₃ SiO- = 7.50ppm OMe ₂ SiO- = -22 ... -23ppm

m, - ·, - -., I MiGbI C = U-I-

'H-NMR spectrum:

IiGGiC-CH

¹³ C-NMR spectrum: I

I i

ppm

130.0 - 143.0 ppm (2 signals)

Claims (1)

1. A process for the preparation of organosilyl, organosiloxanyl or Organopolysiloxanylsubstituierten alkenol compounds of the general formula I, X. R ¹ CaIaCCK ² R ³ OH in the R ¹ = H, alkyl radical having 1 to 10 C atoms or methylol radical, R ² = H, alkyl radical having 1 to 6 C atoms, R ³ = H, alkyl radical having 1 to 6 C atoms or S-hydroxyprcpinyl radical, X = organosilyl radicals having lower alkyl, alkoxy and / or aryl groups, straight-chain, branched-chain and / or cyclic organosiloxanyl radicals having 1 to 20 Si atoms and lower alkyl, alkoxy and / or aryl groups, is straight-chain and / or branched-chain organopolysiloxanyl radicals having 20 to 700Si atoms and lower alkyl, alkoyy and / or aryl groups, characterized in that in a reaction step without protection of the OH groups alkynols of the general formula II,