Additive for rheology improvement of inorganic binders

Patent metadata

Field	Value
Publication number	US-9803053-B2
Application number	US-201415102757-A
Country	US
Kind code	B2
Filing date	Dec 16, 2014
Priority date	Dec 20, 2013
Publication date	Oct 31, 2017
Grant date	Oct 31, 2017

Abstract

The invention concerns a polycondensate containing (I) at least a structural unit, which is an aromatic moiety bearing a polyether side chain comprising 9 to 41 alkylene glycol units, (II) at least a structural unit, which is an aromatic moiety bearing at least one phosphoric acid ester group and (III) at least a methylene unit (—CH 2 —), the polycondensate having a polycondensation degree of 10 to 75. Also concerned are building material mixtures containing said polycondensates and the use as dispersant for inorganic binders.

First claim

The invention claimed is:

1. A polycondensate containing
(I) at least a structural unit, which is an aromatic moiety bearing a polyether side chain comprising alkylene glycol units, with the proviso that the number of ethylene glycol units in the side chain is from 9 to 41 and that the content of ethylene glycol units is higher than 80 mol % with respect to all alkylene glycol units in the polyether side chain,
(II) at least a structural unit, which is an aromatic moiety bearing at least one phosphoric acid ester group and/or its salt, with the proviso that the molar ratio of (I) to (II) is from 0.3 to 4,
(III) at least a methylene unit (—CH 2 —), which is attached to two aromatic structural units Y, where
aromatic structural units Y, independently of one another, are identical or different and are represented by structural unit (I), structural unit (II) or optionally (IV) aromatic structural units of the polycondensate, which are different from structural unit (I) and structural unit (II) and
wherein the polycondensation degree of the polycondensate containing the units (I), (II), (III) and optionally (IV) is in the range from 10 to 75.

2. The polycondensate according to claim 1 , in which the number of ethylene glycol units in the polyether side chain of structural unit (I) is from 9 to 35.

3. The polycondensate according to claim 1 , in which the average molecular weight of the polycondensate is from 5,000 g/mol to 25,000 g/mol.

4. The polycondensate according to claim 1 , in which the structural unit (I) is derived from an alkoxylated aromatic alcohol monomer bearing a hydroxyl group at the end of the polyether side chain.

5. The polycondensate according to claim 1 , in which the structural unit (II) is derived from an aromatic alcohol monomer, which was in a first step alkoxylated and the obtained alkoxylated aromatic alcohol monomer bearing a hydroxyl group at the end of the polyether side chain was in a second step phosphorylated to the phosphoric acid ester group.

6. The polycondensate according to claim 1 , in which the structural unit (I) is a phenyl poly alkylene glycol.

7. The polycondensate according to claim 1 , in which the structural unit (II) is selected from the group of alkoxylated phenol phosphoric acid esters or alkoxylated hydroquinone phosphoric acid esters according to the following general structures (VI) and/or (VII),
—[C 6 H 3 —O-(AO) n —PO 3 M 2 ]—,  (VI)

-[[M 2 O 3 P-(AO) n ]—O—C 6 H 2 —O-[(AO) n —PO 3 M 2 ]]-,  (VII)

n is in both formulae an integer from 1 to 5, A is in both formulae an alkylene with 2 to 5, M independently of one another is identical or different and is H or a cation equivalent.

8. The polycondensate according to claim 1 , in which the molar ratio of ethylene glycol units from structural units (I) to phosphoric acid ester units from structural unit (II) is from 11 to 40.

9. The polycondensate according to claim 1 , in which the molar ratio of the sum of structural units (I) and (II) to the structural units (IV) is higher than 1/1.

10. The polycondensate according to claim 9 , in which the molar ratio of the sum of structural units (I) and (II) to structural unit (IV) is lower than 10/1 and the structural unit (IV) is an aromatic moiety bearing a polyether side chain comprising alkylene glycol units, with the proviso that the number of ethylene glycol units in the side chain of structural unit (IV) is from 42 to 120 and that the content of ethylene glycol units is higher than 80 mol % with respect to all alkylene glycol units in the polyether side chain of structural unit (IV).

11. The polycondensate according to claim 1 , in which the molar ratio of the sum of structural units (I) and (II) to the structural units (III) is from 0.8/1 to 1/0.8.

12. The polycondensate according to claim 1 in a formulation together with further dispersants selected from the group of a) sulfonated melamine-formaldehyde condensates, b) lignosulfonates, c) sulfonated ketone-formaldehyde condensates, d) sulfonated naphthalene-formaldehyde condensates (BNS), e) polycarboxylate ethers (PCE), f) non-ionic copolymers for extending workability to a cementitious mixture containing hydraulic cement and water, wherein the copolymer comprises residues of at least the following monomers:
Component A comprising an ethylenically unsaturated carboxylic acid ester monomer comprising a moiety hydrolysable in the cementitious mixture, wherein the hydrolysed monomer residue comprises an active binding site for a component of the cementitious mixture; and
Component B comprising an ethylenically unsaturated, carboxylic acid ester or alkenyl ether monomer comprising at least one C 2-4 oxyalkylene side group of 1 to 350 units or g) phosphonate containing dispersants according to the following formula
R—(OA) n -N—[CH 2 —PO(OM 2 ) 2 ] 2

whereby
R is H or a saturated or unsaturated hydrocarbon radical, optionally a C1 to C15 alkyl radical,
A is the same or different and independently from each other an alkylene with two to 18 carbon atoms, optionally ethylene and/or propylene, n is an integer from 5 to 500, and
M is H, an alkali metal, 1/2 earth alkali metal and/or an amine and whereby any combination of the further dispersants a) to g) is possible.

13. The polycondensate according to claim 12 , in which the further dispersant in the formulation is f-1) a non-ionic copolymer with a weight average molecular weight M W from 5,000 g/mol to less than 25,000 g/mol for extending workability to a cementitious mixture containing hydraulic cement and water, wherein the copolymer comprises residues of at least the following monomers:
Component A comprising an ethylenically unsaturated carboxylic acid ester monomer comprising a moiety hydrolysable in the cementitious mixture, wherein the hydrolysed monomer residue comprises an active binding site for a component of the cementitious mixture; and
Component B comprising an ethylenically unsaturated, carboxylic acid ester or alkenyl ether monomer comprising at least one C 2-4 oxyalkylene side group of 10 to 70 units.

14. A building material mixture comprising one or more polycondensates according to claim 1 and one or more inorganic binders selected from the group of α-calcium sulfate hemihydrate, β-calcium sulfate hemihydrate, calcium sulfate in the form of anhydrite, slag sand, fly ash, fumed silica, blast furnace slag, natural pozzolanes, burnt oil shale and/or, Portland cement.

15. The building material mixture according to claim 14 comprising aggregates and Portland cement and optionally further binders selected from the group of slag sand, fly ash, fumed silica, blast furnace slag, natural pozzolanes and burnt oil shale, and any combination thereof.

16. A method comprising dosing inorganic binder with the polycondensates according to claim 1 for the dispersion of the inorganic binders, selected from the group of α-calcium sulfate hemihydrate, β-calcium sulfate hemihydrate, calcium sulfate in the form of anhydrite, slag sand, fly ash, fumed silica, blast furnace slag, natural pozzolanes, burnt oil shale and/or Portland cement, optionally wherein the Portland cement is present with a proportion greater than 40% by weight based on the total amount of the inorganic binder.

17. A method comprising dosing concrete with the polycondensates according to claim 1 for the reduction of the plastic viscosity of the concrete.

18. A method comprising dosing polycondensates according to claim 1 in self-compacting concrete with a contents of fines between 300 kg/m 3 to 700 kg/m 3 , the de

Assignees

• Construction Research & Technology Gmbh

Inventors

• Kraus Alexander
• Dengler Joachim
• Gädt Torben
• Moro Sandro
• Bokern Juergen
• Bendale Anil
• Moins Nicolas
• Zeminian Nicoletta

Classifications

• C04B24/32

  Polyethers, e.g. alkylphenol polyglycolether · CPC title

• C04B28/16

  containing anhydrite {, e.g. Keene's cement} · CPC title

• C04B2103/30

  Water reducers, plasticisers, air-entrainers, flow improvers · CPC title

• C08G65/3355 Primary

  having phosphorus bound to carbon and oxygen · CPC title

• C04B24/30

  Condensation polymers of aldehydes or ketones · CPC title