Copolymers having phosphorus group-carrying monomeric units

Patent metadata

Field	Value
Publication number	US-10562999-B2
Application number	US-201615763425-A
Country	US
Kind code	B2
Filing date	Sep 22, 2016
Priority date	Sep 24, 2015
Publication date	Feb 18, 2020
Grant date	Feb 18, 2020

Abstract

A copolymer, in particular a dispersant for solid particles, in particular a dispersant for mineral binder compositions, including a polymer backbone and sidechains bound thereto. Said copolymer includes at least one phosphorus group-carrying monomeric unit M1 and at least one sidechain-carrying monomeric unit M2, the copolymer having, in a direction along the polymer backbone, a non-random distribution of the monomeric units M1 and/or of the monomeric units M2.

First claim

The invention claimed is:

1. A copolymer having a polymer backbone and side chains bonded thereto, comprising at least one phosphorus group-bearing monomer unit M1 and at least one side chain-bearing monomer unit M2, wherein:
the copolymer has a nonrandom distribution of the monomer units M1 and/or the monomer units M2 in a direction along the polymer backbone,
the copolymer has a gradient structure in at least one section AA in a direction along the polymer backbone with respect to the phosphorus group-bearing monomer unit M1 and/or with respect to the side chain-bearing monomer unit M2, and
the copolymer, in addition to the at least one section AA, has a section AB where there is essentially a constant local concentration of the monomers and/or a statistical or random distribution of the monomers over the entire section AB.

2. The copolymer as claimed in claim 1 , wherein the copolymer has a block structure in the section AB.

3. The copolymer as claimed in claim 1 , wherein the phosphorus group-bearing monomer unit M1 is based on a (meth)acrylic ester, (meth)acrylamide, vinyl ether, allyl ether, methallyl ether, and/or isoprenyl ether, each comprising a phosphoric acid group and/or a phosphonic acid group.

4. The copolymer as claimed in claim 1 , wherein the phosphorus group-bearing monomer unit M1 in the copolymer has a structure of formula I:

and the side chain-bearing monomer unit M2 includes a structure of formula II:

where
R 1 , in each case independently, is a group of formula Ia:

and L has a structure of formula Ib:

a=0-5; b=0 or 1; c=0 or 1; d=0-5; e=0 or 1; f=1-10; g=0-5; h=1-5; i=0 or 1; j=0 or 1;
G is —O— or —NH—;
each Q, independently of the others, is hydrogen, an alkyl group having 1-5 carbon atoms, and/or PO 3 M 2 ; and
each K, independently of the others, is hydrogen, a chemical bond, or an alkylene group having 1-3 carbon atoms;
R 2 , R 3 , R 5 and R 6 , in each case independently, are H or an alkyl group having 1 to 5 carbon atoms,
R 4 and R 7 , in each case independently, are H, COOM, or an alkyl group having 1 to 5 carbon atoms,
or R 1 forms a ring together with R 4 to give —CO—O—CO—,
M, independently of one another, represents H + , an alkali metal ion, an alkaline earth metal ion, a di- or trivalent metal ion, an ammonium ion, or an organic ammonium group;
m=0, 1 or 2,
p=0 or 1,
X, in each case independently, is —O— or —NH—,
R 8 is a group of formula -[AO] n —R a
where A=C 2 - to C 4 -alkylene, R a is H, a C 1 - to C 20 -alkyl group, -cycloalkyl group or -alkylaryl group, and
n=2-250.

5. The copolymer as claimed in claim 1 , wherein the copolymer comprises at least one further monomer unit MS of formula III:

where
R 5′ and R 6′ , in each case independently, are H or an alkyl group having 1 to 5 carbon atoms,
R 7′ , in each case independently, is H, —COOM or an alkyl group having 1 to 5 carbon atoms, where each M independently represents H + , an alkali metal ion, an alkaline earth metal ion, a di- or trivalent metal ion, an ammonium ion, or an organic ammonium group,
m′=0, 1 or 2,
p′=0 or 1,
Y, in each case independently, is a chemical bond or —O—;
Z, in each case independently, is a chemical bond, —O— or —NH—;
R 9 , in each case independently, is an alkyl group, cycloalkyl group, alkylaryl group, aryl group, hydroxyalkyl group or an acetoxyalkyl group, each having 1-20 carbon atoms.

6. The copolymer as claimed in claim 1 , wherein a polydispersity of the copolymer is <1.5.

7. The copolymer as claimed in claim 1 , wherein a molar ratio of the monomer units M1 to the monomer units M2 in the copolymer is in a range of 0.5-6.

8. The copolymer as claimed in claim 4 , wherein:
a=0, b=1, c=1, G=—O—, d=1-2, Q=H, e=0 or 1, f=1 and j=0;
R 2 and R 5 , independently of one another, are H, —CH 3 , or mixtures thereof;
R 3 and R 6 , independently of one another, are H or —CH 3 ,
R 4 and R 7 , independently of one another, are H or —COOM, and
X in at least 75 mol % of all monomer units M2 is —O—.

9. The copolymer as claimed in claim 1 , wherein the copolymer is obtained or has been prepared by a controlled free-radical polymerization and/or a living free-radical polymerization.

10. A method comprising: preparing a composition comprising solid particles and a copolymer as described in claim 1 , wherein the copolymer is present in an amount effective to act as a dispersant for the solid particles.

11. A binder composition comprising a mineral binder and at least one copolymer as described in claim 1 .

12. A shaped body obtained by curing a mineral binder composition comprising a copolymer as described in claim 11 after addition of water.

Assignees

• Sika Tech Ag

Inventors

• Weidmann Jürg
• Frunz Lukas
• Glaus Joachim
• Gresser Jürgen

Classifications

• C08F293/005 Primary

  using free radical "living" or "controlled" polymerisation, e.g. using a complexing agent · CPC title

• C04B2103/0063

  obtained by an unusual polymerisation process, e.g. by changing the molar ratio of the different monomers during the polymerisation process (C04B2103/0058 - C04B2103/0061 take precedence) · CPC title

• C08F2438/03

  Use of a di- or tri-thiocarbonylthio compound, e.g. di- or tri-thioester, di- or tri-thiocarbamate, or a xanthate as chain transfer agent, e.g . Reversible Addition Fragmentation chain Transfer [RAFT] or Macromolecular Design via Interchange of Xanthates [MADIX] · CPC title

• C04B2103/0061

  Block (co-)polymers · CPC title

• C04B2103/408

  Dispersants · CPC title