Enzymatically modified lignins
The present invention relates to water-soluble modified lignins preparable by enzymatic reaction of at least one water-insoluble lignin with at least one organic compound which possesses at least one group selected from primary or secondary amino group, hydroxyl group and phenyl group and has an average molecular weight in the range from 75 to 2500 g/mol. The water-soluble modified lignins are preparable under mild conditions in a simple process. They can be used as dispersants for mineral binder compositions, where they act as plasticizers and in so doing prolong the setting time to much less of an extent than the water-insoluble lignins used in their preparation.
1. A water-soluble modified lignin ML, prepared by enzymatic reaction of at least one water-insoluble lignin L with at least one organic compound V, the at least one organic compound V possessing at least one selected from the group consisting of a primary amino group, a secondary amino group, a hydroxyl group and a phenyl group, and has an average molecular weight M n in the range from 75 to 2500 g/mol,
wherein in the enzymatic reaction, at least one enzyme selected from the group consisting of peroxidases and phenol oxidases is present.
2. The water-soluble modified lignin ML according to claim 1 , wherein the organic compound V is selected from the group consisting of
A) compounds of the formula (I),
Z x —R-G-R—W y (I)
where
Z independently at each occurrence is —OH, —NH 2 , O—R 1 or R 1 ,
G is a phenylene or naphthylene radical,
R independently at each occurrence is a covalent bond or a linear or branched, aliphatic hydrocarbon radical having 1 to 8 C atoms and optionally comprising unsaturated fractions,
R 1 independently at each occurrence is an alkyl group having 1 to 4 C atoms,
x is 1 or 2 or 3,
y is 1 or 2 or 3, and
W is —COOM, —SO 3 M, —OSO 3 M, —PO 3 M 2 or —OPO 3 M 2 , where M is H, an alkali metal, an alkaline earth metal, a di- or trivalent metal or an organic or inorganic ammonium;
B) compounds of the formula (II)
where
E is a phenoxy group or a primary amino group,
A and B independently of one another are an alkylene radical having 2 to 4 C atoms,
(n+m) is 1 to 50, and
R 2 is H, an alkyl group having 1 to 8 C atoms, —COOM, —SO 3 M, —OSO 3 M, —PO 3 M 2 or —OPO 3 M 2 ;
C) amino acids; and
D) aliphatic, linear or branched aminosulphonic acids having 2 to 10 C atoms.
3. The water-soluble modified lignin ML according to claim 2 , wherein the compound of the formula (I) is an aromatic compound having at least one sulphonic acid group or carboxylic acid group and at least one amino group bonded to the phenylene or naphthylene radical.
4. The water-soluble modified lignin ML according to claim 1 , wherein the organic compound V is selected from the group consisting of glycine, alanine, glutamic acid, aspartic acid, tyrosine, serine, histidine and arginine.
5. The water-soluble modified lignin ML according to claim 1 , wherein the organic compound V is taurine.
6. The water-soluble modified lignin ML according to claim 1 , wherein the enzymatic reaction is carried out using 0.4 to 15 mmol of organic compound V per gram of water-insoluble lignin L.
7. The water-soluble modified lignin ML according to claim 1 , wherein in the enzymatic reaction the at least one enzyme is selected from the group consisting of laccases or tyrosinases.
8. The water-soluble modified lignin ML according to claim 1 , wherein the enzymatic reaction is carried out in a reaction medium comprising water and optionally at least one organic solvent.
9. The water-soluble modified lignin ML according claim 1 , wherein the enzymatic reaction is carried out in the presence of a mediator.
10. A process for preparing the water-soluble modified lignin ML according to claim 1 , the process comprising enzymatically reacting a water-insoluble lignin L with at least one organic compound V, the organic compound V possessing at least one selected from the group consisting of a primary amino group, a secondary amino group, a hydroxyl group and a phenyl group and having an average molecular weight M n in the range from 75 to 2500 g/mol,
wherein in the step of enzymatically reacting the water-insoluble lignin L with the at least one organic compound, at least one enzyme selected from the group consisting of peroxidases and phenol oxidases is present.
11. A reaction product from the process according to claim 10 , comprising the water soluble modified lignin ML.
12. A method comprising dispersing the water-soluble modified lignin ML according to claim 1 in a composition comprising mineral binders.
13. A composition comprising
at least one mineral binder,
at least one water-soluble modified lignin ML according to claim 1 , and optionally water.
14. A shaped body obtained by setting and curing the composition according to claim 13 after contact thereof with water.
15. A dispersant for mineral binders, comprising at least one water-soluble modified lignin ML according to claim 1 .
16. The process for preparing the water-soluble modified lignin ML according to claim 10 , wherein the at least one enzyme is selected from the group consisting of laccases and tyrosinases.