Copolymer as a water-reducing agent in a hydraulic composition and use of copolymers for improving the early mechanical strength of a hydraulic composition

Patent metadata

Field	Value
Publication number	US-10501371-B2
Application number	US-201715705324-A
Country	US
Kind code	B2
Filing date	Sep 15, 2017
Priority date	Mar 16, 2015
Publication date	Dec 10, 2019
Grant date	Dec 10, 2019

Abstract

Novel copolymers obtained by polymerisation a mixture of monomers comprising: at least one anionic monomer (a) comprising a polymerisable unsaturated function and a carboxylic group; and at least one monomer (b) of formula (I):

H 2 C═C(—R 1 )—(CH 2 ) p —O-[(EO) n —(PO) m ]—H  (I)

where [(EO) n —(PO) m ] represents a polyalkoxylated chain consisting of ethoxylated units EO and propoxylated units PO, distributed into blocks, alternating or statistical, the molar proportion of the ethoxylated units in the polyalkoxylated chain (n)/(m+n) being greater than or equal to 70% and strictly less than 90%. In addition, hydraulic composition, for example concrete compositions, comprising such copolymers, and the use of said copolymers as water-reducing agents in hydraulic compositions and for increasing the early mechanical strength of a hydraulic composition.

First claim

The invention claimed is:

1. A copolymer obtained by polymerization of a monomer mixture comprising:
at least one anionic monomer (a) comprising a polymerizable unsaturated function and a carboxylic group; and
at least one monomer (b) of formula (I):
H 2 C═C(—R 1 )—(CH 2 ) p —O-[(EO) n —(PO) m ]—H  (I)

wherein:
R 1 represents a hydrogen atom or a CH 3 group;
p is 1 or 2;
[(EO) n —(PO) m ] represents a polyalkoxyl chain made of ethoxyl units EO and propoxyl units PO, distributed in blocks, alternately or randomly;
m and n represent integers ranging between 1 and 250, the sum of m and n being greater than or equal to 10, with the proviso that the mole proportion of the ethoxyl units in the polyalkoxyl chain (n)/(m+n) is greater than or equal to 70% and less than 90%,

wherein the monomer (b) represents from 1 to 18 mol % of the total mole number of monomers that constitute said copolymer.

2. The copolymer of claim 1 , wherein the monomer (b) has formula (I′):
H 2 C═C(—R 1 )—CH 2 —O-[(EO) n —(PO) m ]—H  (I′).

3. The copolymer of claim 1 , wherein monomer (b) has formula (II):
H 2 C═C(—CH 3 )—CH 2 —O-[(EO) n —(PO) m ]—H  (II).

4. The copolymer of claim 1 , wherein the mole proportion of the ethoxyl units in the polyalkoxyl chain of monomer (b) is between 70% and 88%.

5. The copolymer of claim 1 , wherein the total number of ethoxyl and propoxyl units (m+n) of the polyalkoxyl chain of the monomer (b) is between 10 and 150.

6. The copolymer of claim 1 , wherein the monomer (b) represents from 1 to 16.6 mol % of the total mole number of monomers that constitute said copolymer.

7. The copolymer of claim 1 , wherein the anionic monomer is at least one selected from the group consisting of acrylic acid, methacrylic acid, maleic acid, itaconic acid, and crotonic acid.

8. The copolymer of claim 1 , wherein the monomer (a) represents from 82 to 99 mol % of the total mole number of monomers that constitute said copolymer.

9. The copolymer of claim 1 , wherein the monomer mixture further comprises at least one further monomer (c) selected from the group consisting of:
2-acrylamino-2-methylpropane sulfonic acid (AMPS);
a vinylsulfonate;
an amine;
an ester containing a hydroxyl group;
an alkylene glycol acrylate or methacrylate phosphate;
an acrylamide or methacrylamide;
a phosphonic monomer;
a macromonomer of formula (VI):
R a -[(EO) q —(PO) r —(BO) s ]—R a ′  (VI)

wherein:
[(EO) q —(PO) r —(BO) s ] represents a polyalkoxyl chain made of alkoxyl units, distributed in blocks, alternately or randomly, chosen from ethoxyl units EO, propoxyl units PO, and butoxyl units BO;
q, r and s represent, independently of each other, 0 or an integer ranging between 1 and 250, the sum of m, n and p being between 10 and 250;
R a represents a radical chosen from the group consisting of acrylic esters, methacrylic esters and a mixture of these esters; and
R a ′ represents hydrogen or an alkyl group containing from 1 to 4 carbon atoms:

a hydrophobic monomers of formula (VII):
R b -[(EO) t —(PO) u —(BO) v ]—R b ′  (VII)

wherein:
[(EO) t —(PO) u —(BO) v ] represents a polyalkoxyl chain made of alkoxyl units, distributed in blocks, alternately or randomly, chosen from ethoxyl units EO, propoxyl units PO, and butoxyl units BO;
t, u and v represent, independently of each other, 0 or an integer ranging between 1 and 250, the sum of m, n and p being between 10 and 250;
R b represents a radical chosen from the group consisting of acrylic esters, methacrylic esters and a mixture of these esters; and
R b ′ represents an alkyl group containing from 8 to 40 carbon atoms; and
a crosslinking monomer.

10. A hydraulic composition comprising a copolymer of claim 1 .

11. A water reducing agent comprising a copolymer of claim 1 .

12. A method for reducing water in a hydraulic composition, the method comprising:
incorporating a copolymer according to claim 1 into a hydraulic composition comprising water, thereby reducing the water content of the hydraulic composition by at least 5% by weight.

13. The method of claim 12 , wherein the water content is reduced by at least 12% by weight.

14. A method for increasing early mechanical strength of a hydraulic composition, the method comprising:
incorporating, into a hydraulic composition, at least one copolymer obtained by polymerization of a monomer mixture comprising:
at least one anionic monomer (a) comprising a polymerisable unsaturated group and a carboxylic group; and
at least one monomer (b) of formula (I):
H 2 C═C(—R 1 )—(CH 2 ) p —O-[(EO) n —(PO) m ]—H  (IA)

wherein:
R 1 represents a hydrogen atom or a CH 3 group,
p is equal to 1 or 2,
[(EO) n —(PO) m ] represents a polyalkoxylated chain constituted of ethoxylated units EO and propoxylated units PO, distributed in blocks, alternating or random and
m and n represent integers varying between 1 and 250, the sum of m and n being greater than or equal to 10, provided that the molar proportion of the ethoxylated units in the polyalkoxylated chain (n)/(m+n) is greater than or equal to 70% and less than 90%,

wherein the monomer (b) represents from 1 to 18 mol % of the total mole number of monomers that constitute said copolymer.

15. The method of claim 14 , wherein a compressive strength of the hydraulic composition at 1 day, measured according to EN 12390-3 standard, is greater than or equal to 155% of the value of the compressive strength of the hydraulic composition devoid of the copolymer.

16. The method of claim 14 , wherein the monomer (b) has formula (IA′):
H 2 C═C(—R 1 )—CH 2 —O-[(EO) n —(PO) m ]—H  (IA′).

17. The method of claim 14 , wherein the monomer (b) has formula (II):
H 2 C═C(—CH 3 )—CH 2 —O-[(EO) n —(PO) m ]—H  (II).

18. The method of claim 14 , wherein the total number of ethoxylated and propoxylated units (m+n) of the polyalkoxylated chain of the monomer (b) is between 10 and 150.

19. The method of claim 14 , wherein the monomer (b) represents from 1 mol % to 16.6 mol % of the total mole number of monomers that constitute the copolymer.

20. The method of claim 14 , wherein the anionic monomer (a) is at least one selected from the group consisting of acrylic acid, methacrylic acid, maleic acid, itaconic acid, and crotonic acid.

Assignees

• Coatex Sas

Inventors

• Platel David
• Magny Benoit
• Suau Jean-Marc
• Champagne Clementine

Classifications

• C04B28/02

  containing hydraulic cements other than calcium sulfates · CPC title

• C04B2103/302

  Water reducers · CPC title

• C04B24/2647 Primary

  containing polyether side chains · CPC title

• C08F220/06

  Acrylic acid; Methacrylic acid; Metal salts or ammonium salts thereof · CPC title

• C04B14/06

  Quartz; Sand · CPC title