Alkoxylation products and process for preparing them by means of DMC catalysts
View Patent ↗Novel alkoxylation products containing lateral hydroxyl groups or bearing lateral C—C double bonds and a process for preparing them by means of an alkoxylation reaction of halogenated alkylene oxides using double metal cyanide (DMC) catalysts and subsequent elimination of chlorine.
1. A compound which includes:
a structural element [—CH 2 —CH(CH 2 OH)—O—] and/or a structural element [—CH 2 —C(═CH 2 )—O—];
wherein the compound has the formula (I):
A-[O—(CH 2 —CHR—O—) n —(CH 2 —CH(CH 2 OH)—O—) m1 —(CH 2 —C(═CH 2 )—O—) m2 —(CH 2 —CH(CH 3 )—O—) o —H] a1 (I)
where a1 is from 1 to 8;
where A is either hydrogen, or a radical, of an organic starter compound, having at least one carbon atom;
where the radicals R are each, independently of one another, either hydrogen, CH 2 —Cl, an alkyl group having 2-18 carbon atoms, or an aromatic radical;
where (a1×m1) is from 0 to 50;
where (a1×m2) is from 0 to 50;
where (a1×n) is from 0 to 200;
where (a1×o) is from 1 to 1000;
where the sum (a1×(m1+m2)) is from 2 to 50; and
where (a1×m1) is 2 or greater than 2 when (a1×m2) is zero.
2. A compound according to claim 1 ;
wherein the molar proportion of the units having the index m 2 is from 20 to 100% based on the sum of the units having the indices m 1 and m 2 , which adds up to 100%.
3. A compound according to claim 2 ;
wherein the molar proportion of the units having the index m 2 is from 30 to 90% based on the sum of the units having the indices m 1 , and m 2 , which adds up to 100%.
4. A compound according to claim 1 ;
wherein the compounds of the formula (I) have an oxypropylene group (index o) as last monomer unit.
5. A compound according to claim 1 ;
wherein the radical A is a radical of a monohydric or polyhydric polyether alcohol and/or a radical of a monohydric or polyhydric alcohol.
6. A compound according to claim 1 ;
wherein the compound has a weight average molar mass of from 200 to 50000 g/mol.
7. A process for preparing compounds comprising the structural element [—CH 2 —CH(CH 2 OH)—O—] and/or the structural element [—CH 2 —C(═CH 2 )—O—] using double metal cyanide catalysts, the process comprising:
process step 1, which includes:
reacting:
(a) one or more compounds of the formula (II):
A—OH (II)
where A=hydrogen or an organic radical having at least one carbon atom;
with:
(b) epichlorohydrin and propylene oxide and optionally one or more further alkylene oxides having from 2 to 18 carbon atoms;
in the presence of:
(c) a double metal cyanide catalyst ;
at a temperature of from 60 to 250° C. and a pressure of from 0.02 bar to 100 bar (absolute) to give an alkoxylation product having one or more chemically bound chlorine atoms; and
process step (2), which includes:
reacting the chlorinated alkoxylation product obtained in process step 1), with one or more metal hydroxide or metal alkoxide compounds, at a temperature of 30-200° C. with complete or partial elimination of the organically bound chlorine;
wherein the reacting optionally takes place in the presence of water;
wherein the reacting optionally takes place in the presence of organic solvents; and
wherein the reacting optionally takes place in the presence of phase transfer catalysts;
wherein the process optionally further comprises process (3), which includes:
work-up of the reaction product by at least one of:
(a) neutralization by means of an inorganic or organic acid;
(b) distillation of water and/or solvent;
(c) removal of chloride salts by phase separation; and
(d) filtration.
8. The process according to claim 7 ;
wherein at least one of sodium hydroxide, potassium hydroxide, ethanolic or methanolic solutions of NaOH or KOH, and mixtures thereof, is used as metal hydroxide; and/or
wherein at least one of sodium methoxide, potassium methoxide, methanolic solutions, and mixtures thereof; is used as metal alkoxide.
9. The process according to claim 8 ;
wherein at least one of a sodium hydroxide solution, a potassium hydroxide solution, a sodium methoxide solution, a potassium methoxide solution, and mixtures thereof, having a concentration of from 10 to 50% by weight is used.
10. The process according to claim 7 ;
wherein the hydroxide and/or alkoxide is used in an equimolar amount or a molar excess based on the bound chlorine in the alkoxylation product.
11. The process according to claim 10 ;
wherein from 1.0 mol to 3 mol of hydroxide or alkoxide is used per 1 mol of chlorine.
12. The process according to claim 7 ;
a compound according to claim 1 is prepared.
13. The process according to claim 7 ;
wherein a composition is obtained which comprises a compound including:
a structural element [—CH 2 —CH(CH 2 OH)—O] and/or a structural element [—CH 2 —C(═CH 2 )—O—];
wherein the compound has the formula (I):
A-[O—(CH 2 —CHR—O—) n —(CH 2 —CH(CH 2 OH)—O—) m1 —(CH 2 —C(═CH 2 )—O—) m2 —(CH 2 —CH(CH 3 )—O—) o —H] a1 (I)
where a1 is from 1 to 8;
where A is either hydrogen or a radical of an organic starter compound, having at least one carbon atom;
where the radicals R are each, independently of one another, either hydrogen, CH 2 —Cl, an alkyl group having 2-18 carbon atoms, or an aromatic radical;
where (a1×m1) is from 0 to 50;
where (a1×m2) is from 0 to 50;
where (a1×n) is from 0 to 200;
where (a1×o) is from 1 to 1000;
where the sum (a1×(m1+m2)) is from 2 to 50; and
where (a1×m1) is 2 or greater than 2 when (a1×m2) is zero.
14. A composition which includes a compound according to claim 1 .