WO2004074346A1

WO2004074346A1 - Method for the production of polyglycerol ethers by directly reacting polyglycerols and alcohols

Info

Publication number: WO2004074346A1
Application number: PCT/EP2004/001349
Authority: WO
Inventors: Ralf Zerrer; Franz-Xaver Scherl
Original assignee: Clariant Gmbh
Priority date: 2003-02-20
Filing date: 2004-02-13
Publication date: 2004-09-02
Also published as: DE10307172A1

Abstract

The invention relates to a method for the production of polyglycerol ethers of formula I (I) wherein the radicals R1, R2 and R3 are identical or different and are independent from each other and represent hydrogen; (C1-C30)-alkyl, optionally, substituted by 1 - 3 (C1-C4)-alkyl-or (C1-C4)-alkoxyl groups; (C2-C30)-alkenyl, optionally sulphonated and, optionally, substituted by 1 - 3 (C1-C4)-alkyl- or (C1-C4)-alkoxyl groups; phenyl, optionally, substituted by 1 - 3 (C1- c4)-alkyl- or (C1-C4)-alkoxyl groups; napthyl, optionally, substituted by 1 - 3 (C1-C4)-alkyl-or (C1-C4)-alkoxyl groups; groups of formulae represent R4R5N-(CH2)y-; HO-(CH2)y-; -(AO)zH; -SO3H; -SO3-X+; -PO3H2; -PO32-X+; -CR2-COOR'; -CR2-COO-X+; -CO-R6-COOH; -CO-R6-COO-X+;-C(R )2C(R )2C(R)2-N(R )2;-C( R)2C(R )2C(R )2-N((AO)ZH)2;-[CH2CH(O(AO)ZH)CH2O]N-R1; whereby R represents H and/or C1- C4-alkyl; R' means H or (C1-C10)-alkyl, (C2-C30)-alkenyl, optionally sulphonated; R4 and R5 which can be equal or different, represent hydrogen, (C1-C10)-alkyl, (C2-C30)-alkenyl, optionally sulphonated, or a group of the formula -(AO)zH; R6 represents (C1-C10)-alkene, (C2-C30)-alkene, optionally sulphonated; X+ represents Na+, K+, Ca2+or N(R7)4+, wherein R7 represents H or (C1-C10)-alkyl, preferably (C1-C4)-alkyl; x represents a number between 0- 15; y represents a number between 4 - 6; z represents a number between 0 - 30, preferably 1 - 5; A represents an alkene group, preferably a group -C2H4-, -C3H6- or C4H8-; n represents a number between 4 - 40, preferably 5 - 20, especially 10 - 20, and the indices represent p1, q1, r1, p2, q2, r2, p3, q3 and r3 for numbers between 0 - 500 with the proviso that at least one of the radicals R1, R2 and R3 of the compounds of formula (I) represents a carbon/hydrogen group, preferably (C1-C30)-alkyl by reacting polyglycerol with fatty alcohol in the presence of a strong acid as a catalyst.

Description

description

Process for the preparation of polyglycemethem by direct reaction of polyglycerols and alcohols

The production of polyglycerol ethers described in the literature is based on the reaction of polyglycerols with glycidyl ethers, as claimed in JP 09235 246. FR 2407 979 describes the preparation of polyglycerol ethers from polyglycerols and alkylglycidyl ethers and their use as surfactants.

Due to the greater availability of alcohols, especially industrial fatty alcohols, in comparison to corresponding glycidyl ethers, a direct etherification of polyglycerols with fatty alcohols would be advantageous. Problems in attempts to manufacture this direct condensation have so far failed in particular due to the immiscibility of polyglycerols and in particular the hydrophobic fatty alcohols.

Surprisingly, it has now been found that the direct etherification of polyglycerols with fatty alcohols is possible using a suitable catalyst system.

The invention relates to a process for the preparation of polyglycerol ethers of the formula I.

RO - (AO) _p1 (AO) _q1 (AO) _r1 - (CH ₂ CHCH ₂ O) _n - (AO ^ AO ^ AO) * - R

(D

O - (AO) _p2 (AO) _q2 (AO) _l2 - R ²

wherein

the radicals R, R and R are independently the same or different and are hydrogen; (-C-C ₃₀ ) alkyl, optionally substituted by 1 to 3 (CC ₄ ) alkyl or (-C-C ₄ ) alkoxy groups;

(C ₂ -C ₃ o) alkenyl, optionally sulfonated and optionally by 1 to 3

(CC ₄ ) alkyl or (-CC ₄ ) alkoxy groups substituted; Phenyl, optionally substituted by 1 to 3 (-CC ₄ ) alkyl or (-C-C ₄ ) alkoxy groups;

Naphthyl, optionally substituted by 1 to 3 (-CC ₄ ) alkyl or (-C-C ₄ ) alkoxy groups;

Groups of the formulas RR ⁵ N- (CH ₂ ) _y -; HO- (CH ₂ ) _y -; - (A0) ₂ H; -SO ₃ H; -SO ₃ ^" X ⁺ ; -PO ₃ H ₂ ; -PO ₃ ^2" X ⁺ ; -CR ₂ -COOR ^' ; -CR ₂ -COO-χ ⁺ ; -CO-R ⁶ -COOH; -CO-R ⁶ -COO ^" X ⁺ ;

-C (R) ₂ C (R) ₂ C (R) ₂ -N (R) ₂ ; -C (R) ₂ C (R) ₂ C (R) ₂ -N ((AO) ₂ H) ₂ ;

- [CH ₂ CH (O (AO) _z H) CH ₂ O] _n - R ¹ ; in which

R represents H and / or C to C ₄ alkyl; R ^'is H or (CrCιo) alkyl, (C ₂ -C ₃₀ ) alkenyl, optionally sulfonated;

R ⁴ and R ⁵ , which may be the same or different, for hydrogen, (C ₁ -C ₁₀ ) -

Alkyl, (C ₂ -C ₃₀ ) alkenyl, optionally sulfonated, or for a group of the formula

- (AO) _z H;

R ^{6 represents} (-C-Cιo) alkylene, (C2-C ₃₀ ) -alkenylene, optionally sulfonated; X ^{+ is} Na ⁺ , K ⁺ , Ca ²⁺ or N (R ⁷ ) ₄ ⁺ , where R ^{7 is} H or (CrC ₁₀ ) alkyl, preferably (CrC ₄ ) alkyl; x represents a number from 0 to 15; y represents a number from 4 to 6; z represents a number from 0 to 30, preferably 1 to 5; A represents an alkylene group, preferably a group -C ₂ H ₄ -, -C ₃ H ₆ - or -C ₄ H ₈ -; n stands for a number from 4 to 40, preferably 5 to 20, in particular 10 to 20; and the indices p1, q1, r1, p2, q2, r2, p3, q3 and r3 stand for numbers from 0 to 500; with the proviso that at least one of the radicals R ¹ , R ² and R ³ he compounds of formula (I) is a hydrogen carbon group, preferably (-C-C ₃₀ ) alkyl; by reacting polyglycerol with fatty alcohol in the presence of a strong acid as a catalyst.

The polycondensation of glycerol takes place in a known manner.

For this purpose, glycerol is heated to 200-280 ° C. in the presence of acidic catalysts, for example HCl, H ₂ SO, sulfonic acids or H ₃ PO _4, or in the presence of alkaline catalysts, such as sodium hydroxide, potassium hydroxide, alkali metal alcoholates, alkali metal carbonates, alkali metal bicarbonates in the absence of water , With the discharge of condensation water, the polyglycerol is formed within 5 to 15 hours with an average degree of condensation of 2 to 100, preferably 3-35, glycerol units.

To produce polyglycerol ethers, polyglycerols or alkoxylated polyglycerols with fatty alcohol in the presence of an acid catalyst, for example H ₂ SO ₄ , p-toluenesulfonic acid or an acid catalyst system, for example H ₂ SO ₄ / H ₃ P0, are preferably at 120 ° C. to 170 ° C. , 5 h to 10 h with discharge of condensation water. The reaction is controlled by determining the hydroxyl number, which is preferably between 400 and 1000 mgKOH / g after the reaction has ended.

₄ fatty alcohols ₂₂ fatty alcohols, in particular Cι ₂ -Cι from - Preferably, the radicals R ^1, R ² and R ³ are derived independently from C. ₈

The polyglycerol ethers produced by the process according to the invention can be modified by alkoxylation, sulfation, phosphating, amination etc. by the standard methods known to the person skilled in the art.

General manufacturing method

A) Polymerization of the Glycerin to Oligoglycerins or Polyglycerols: The polymerization of the glycerol to oligoglycerols or polyglycerols can be carried out as standard in a stirrer with water separator at 240 to 270 ° C and nitrogen passage. 50% sodium hydroxide solution in a concentration range of 0.1 to 0.4% by weight is used as the catalyst. After 5-20 hours, depending on the desired degree of polymerization, the polymerization is ended. A sample is taken and the OH number is determined. The average molar mass of the oligo- or polyglycerols can be calculated from the OH number.

B) Preparation of polyglycerol ether

The molten polyglycerol is mixed in a stirred tank with a water separator with the fatty alcohol or alkoxylated fatty alcohol in the desired molar ratio and the reaction mixture is heated to 100 ° C. An acidic catalyst system is added and the temperature is raised to 120 ° C to 200 ° C. Over a period of 3 to 5 hours, the water formed during the reaction is removed, which leads to the formation of a homogeneous reaction product.

Examples

Production examples of polyglycerol ethers are described below without restricting the invention thereto.

Production of polyglycerol with n = 9

2000 g of glycerol and 6.0 g of NaOH (50%) were heated to 270 ° C. with stirring in a nitrogen inlet and water separator. After a reaction time of 9 hours and a discharge of 444 g of water, a sample was taken and the OH number was determined. The OH number determined was 890 mg KOH / g. This corresponds to an average degree of condensation n of 9.0 glycerol units.

The polyglycerols with n = 7 and n = 15 are prepared in an analogous manner with a correspondingly shorter or longer reaction time. Production of polyglycerol ether from polyglycerol and Cι ₂ -i4 fatty alcohol

C ₁₂ fatty alcohol -i ₄ (Lorol ^® DD, avg M.W. .: 270 g / mol.) Is added to a polyglycerol having an average degree of condensation of 15, 9 or 7 glycerol units in the molar ratio 1: 1 are added and the reaction mixture to 100 ° C heated. An acidic catalyst system is added (see Table 1) and the temperature is raised to 150 ° C. Over a period of 4 hours, the water formed during the reaction is removed from the circuit, which leads to the formation of a homogeneous reaction product.

Table 1

Claims

claims:

1. Process for the preparation of polyglycerol ethers of the formula I.

RO - (AO) _p1 (AO) _q1 (AO) _r1 - (CH ₂ CHCH ₂ O) _n - (AO) _p3 (AO) _q3 (AO) _r3 - R

(I)

O - (AO) _p2 (AO) _q2 (AO) _r2 - R ²

wherein the radicals R ¹ , R ² and R ^{3 are} independently the same or different and for

Hydrogen; (CrC ₃ o) alkyl, optionally by 1 to 3 (-CC ₄ ) alkyl or

(-C-C ₄ ) alkoxy groups substituted;

(C ₂ -C ₃ o) alkenyl, optionally sulfonated and optionally by 1 to 3

(CrC ₄ ) alkyl or (C 1 -C ₄ ) alkoxy groups substituted;

Phenyl, optionally substituted by 1 to 3 (-C ₄ ) alkyl or (CrC ₄ ) alkoxy groups;

Naphthyl, optionally substituted by 1 to 3 (CrC ₄ ) alkyl or (-C-C ₄ ) alkoxy groups;

Groups of the formulas R ⁴ R ⁵ N- (CH ₂ ) _y -; HO- (CH ₂ ) _y -; - (AO) _z H; -S0 ₃ H; -SO ₃ ^" X ⁺ ;

-PO ₃ H ₂ ; -PO ₃ ^{2 "} X ⁺ ; -CR ₂ -COOR \ - -CR ₂ -COO ^" X ⁺ ; -CO-R ⁶ -COOH; -CO-R ⁶ -COO-χ ⁺ ; -C (R) ₂ C (R) ₂ C (R) ₂ -N (R) ₂ ; -C (R) ₂ C (R) ₂ C (R) ₂ -N ((AO) _z H) ₂ ;

- [CH ₂ CH (O (AO) ₂ H) CH ₂ 0] _n - R ¹ ; in which

R represents H and / or C to C ₄ alkyl;

R 'H or (-C-Cιo) alkyl, (C ₂ -C ₃ o) alkenyl, optionally sulfonated, means; R ⁴ and R ⁵ , which may be the same or different, for hydrogen, (C ₁ -C ₁₀ ) -

Alkyl, (C ₂ -C ₃ o) alkenyl, optionally sulfonated, or for a group of the formula

- (AO) stand;

R ^{6 represents} (CrCιo) alkylene, (C ₂ -C ₃₀ ) alkenylene, optionally sulfonated;

X ^{+ stands} for Na ⁺ , K ⁺ , Ca ²⁺ or N (R ⁷ ) ₄ ⁺ , where R ^{7 stands} for H or (-CC ₁₀ ) -alkyl, preferably (-C-C) -alkyl; x represents a number from 0 to 15; y represents a number from 4 to 6; z represents a number from 0 to 30, preferably 1 to 5;

A represents an alkylene group, preferably a group -C ₂ H ₄ -, -C ₃ H ₆ - or -CH ₈ -; n stands for a number from 4 to 40, preferably 5 to 20, in particular 10 to 20; and the indices p1, q1,, p2, q2, r2, p3, q3 and r3 stand for numbers from 0 to 500; with the proviso that at least one of the radicals R ¹ , R ² and R ^{3 of} the compounds of the formula (I) represents a hydrogen carbon group, preferably (C 1 -C ₃₀ ) alkyl; by reacting polyglycerol with fatty alcohol in the presence of a strong acid as a catalyst.

2. The method of claim 1, wherein the catalyst is selected from H ₂ S04 H ₂ SO ₄ / H ₃ PO ₄ or p-toluenesulfonic acid.

3. The method according to claim 1 and / or 2, wherein a C _δ - ₂₂ fatty alcohol is reacted in the presence of a strong acid as a catalyst with polyglycerol.

4. The method according to claim 3, wherein it is a -C ₂ -C ₄ fatty alcohol.

5. The method according to one or more of claims 1 to 4, wherein the polyglycerol comprises 3 to 35 glycerol units.