# US 10,202,495 B2 · Enzymatically modified lignins

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- Number: US 10,202,495 B2
- Document ID: US10202495B2
- Status: Granted
- Kind: B2
- Application number: 15/459,459
- Filed: 2017-03-15
- Published: 2017-09-21
- Granted: 2019-02-12
- Earliest claimed: 2016-03-15
- Assignees: Sika Technology AG; Empa
- Applicants: Sika Technology AG; Empa
- Inventors: Irene Schober; Michael Richter; Tobias Heck; Dagmara Jankowska
- Web page: https://patentgrep.com/patent/US10202495B2

## CPC

- C08H 6/00: {Macromolecular compounds derived from lignin, e.g. tannins, humic acids}
- C04B 24/18: Lignin sulfonic acid or derivatives thereof, e.g. sulfite lye
- C04B 24/24: Macromolecular compounds (C04B24/14 takes precedence; macromolecular compounds comprising sulfonate or sulfate groups C04B24/16)
- C04B 28/04: Portland cements
- C12P 7/22: aromatic
- C12P 19/04: Polysaccharides, i.e. compounds containing more than five saccharide radicals attached to each other by glycosidic bonds
- C12Y 110/03002: Laccase (1.10.3.2)
- C04B 2103/30: Water reducers, plasticisers, air-entrainers, flow improvers
- C04B 2103/40: Surface-active agents, dispersants
- C04B 2103/408: {Dispersants}
- C08H: DERIVATIVES OF NATURAL MACROMOLECULAR COMPOUNDS (polysaccharides C08B; natural rubber C08C; natural resins or their derivatives C09F; bituminous materials C10)
- C04B: LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE {(roofing granules E04D7/005)}; CERAMICS (devitrified glass-ceramics C03C10/00); REFRACTORIES; TREATMENT OF NATURAL STONE
- C12P: FERMENTATION OR ENZYME-USING PROCESSES TO SYNTHESISE A DESIRED CHEMICAL COMPOUND OR COMPOSITION OR TO SEPARATE OPTICAL ISOMERS FROM A RACEMIC MIXTURE {(brewing of beer C12C; producing vinegar C12J; producing specific peptides or proteins C07K; producing enzymes C12N9/00; DNA or RNA concerning genetic engineering, vectors, e.g. plasmids, or their isolation, preparation or purification C12N15/00; measuring or testing processes involving enzymes or microorganisms C12Q; measuring or testing processes involving nucleic acid amplification reactions C12Q1/6844; fermentation processes to form a food composition, A21 or A23; compounds in general, see the relevant compound class, e.g. C01, C07)}
- C12Y: ENZYMES

## Abstract

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.

## Claims

### Claim 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 Mn 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.

### Claim 2 (depends on 1)

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),
Zx—R-G-R—Wy (I)
where
Z independently at each occurrence is —OH, —NH2, O—R1 or R1,
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,
R1 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, —SO3M, —OSO3M, —PO3M2 or —OPO3M2, 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
R2 is H, an alkyl group having 1 to 8 C atoms, —COOM, —SO3M, —OSO3M, —PO3M2 or —OPO3M2;
C) amino acids; and
D) aliphatic, linear or branched aminosulphonic acids having 2 to 10 C atoms.

### Claim 3 (depends on 2)

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.

### Claim 4 (depends on 1)

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.

### Claim 5 (depends on 1)

The water-soluble modified lignin ML according to claim 1, wherein the organic compound V is taurine.

### Claim 6 (depends on 1)

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.

### Claim 7 (depends on 1)

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.

### Claim 8 (depends on 1)

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.

### Claim 9 (depends on 1)

The water-soluble modified lignin ML according claim 1, wherein the enzymatic reaction is carried out in the presence of a mediator.

### Claim 10 (depends on 1)

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 Mn 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.

### Claim 11 (depends on 10)

A reaction product from the process according to claim 10, comprising the water soluble modified lignin ML.

### Claim 12 (depends on 1)

A method comprising dispersing the water-soluble modified lignin ML according to claim 1 in a composition comprising mineral binders.

### Claim 13 (depends on 1)

A composition comprising
at least one mineral binder,
at least one water-soluble modified lignin ML according to claim 1, and optionally water.

### Claim 14 (depends on 13)

A shaped body obtained by setting and curing the composition according to claim 13 after contact thereof with water.

### Claim 15 (depends on 1)

A dispersant for mineral binders, comprising at least one water-soluble modified lignin ML according to claim 1.

### Claim 16 (depends on 10)

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.