Method for producing aqueous dispersions

Patent metadata

Field	Value
Publication number	US-11427728-B2
Application number	US-201716338592-A
Country	US
Kind code	B2
Filing date	Oct 6, 2017
Priority date	Oct 7, 2016
Publication date	Aug 30, 2022
Grant date	Aug 30, 2022

Abstract

The present invention relates to a process for preparing an aqueous dispersion of polymer particles by radical aqueous emulsion polymerization and also to the use thereof in paints, paper coatings, foams, crop protection compositions, cosmetic compositions, liquid inks, or thermoplastic molding compounds.

First claim

The invention claimed is:

1. A process for preparing an aqueous dispersion of polymer particles by radical aqueous emulsion polymerization, the process comprising:
i) preparing an aqueous dispersion of a seed polymer by radical aqueous emulsion polymerization of an aqueous monomer emulsion comprising:
a) 25.0 to 99.9 wt % of at least one nonionic, monoethylenically unsaturated monomer M1 having a water-solubility ≤50 g/L at 20° C.,
b) 0 to 15.0 wt % of one or more monoethylenically unsaturated monomers M2 selected from the group consisting of a monomer M2a which comprises at least one anionic or anionogenic group and a neutral monomer M2b which has a water-solubility of >50 g/L at 20° C., and a mixture thereof,
c) 0.1 to 60.0 wt % of at least one polyalkylene oxide-containing substance, based on a total weight of the monomers used in said preparing i) and of the polyalkylene oxide-containing substance;

ii) preparing an aqueous dispersion of a swell-seed by radical aqueous emulsion polymerization of an aqueous suspoemulsion comprising:
d) 5 to 99.9 wt % of at least one nonionic, monoethylenically unsaturated monomer M3 having a water-solubility ≤50 g/L at 20° C.,
e) 0 to 75.0 wt % of one or more monoethylenically unsaturated monomers M4 selected from the group consisting of a monomer M4a which comprises at least one anionic or anionogenic group and a neutral monomer M4b which has a water-solubility of >50 g/L at 20° C., and a mixture thereof, and
f) 0.1 to 20.0 wt % of the seed polymer obtained in said preparing i), based on a total weight of the monomers used in said preparing ii) and of the seed polymer;

iii) subsequently forming at least one polymer shell by radical aqueous emulsion polymerization of at least one shell-forming monomer M5 in the presence of the swell-seed obtained in said preparing ii), to form an aqueous dispersion of emulsion polymer particles; and
iv) subsequently neutralizing the aqueous dispersion obtained in said forming iii) to a pH of at least 7.5 with at least one base;

wherein the polyalkylene oxide-containing substance is a polysiloxane-polyalkylene oxide copolymer, and
wherein the aqueous dispersion of polymer particles has a whiteness after storing at 50° C. for 6 weeks of greater than 79.

2. The process according to claim 1 , wherein a volume median of particle size of the seed polymer, determined by hydrodynamic fractionation, in an unswollen state ranges from 10 to 100 nm.

3. The process according to claim 1 , wherein a volume median of particle size of the swell-seed, determined by hydrodynamic fractionation, in an unswollen state ranges from 50 to 300 nm.

4. The process according to claim 1 , wherein the polysiloxane-polyalkylene oxide copolymer is at least one selected from the group consisting of a polysiloxane-polyalkylene oxide graft copolymer, and a polysiloxane-polyalkylene oxide graft copolymer with α-ω structure.

5. The process according to claim 1 , wherein the polysiloxane-polyalkylene oxide copolymer is a polysiloxane-polyalkylene oxide copolymer, which is a polysiloxane-polyalkylene oxide graft copolymer of formula (I):

where
R, R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , R 9 independently of one another are H or alkyl, OH, O-alkyl, allyl, O-allyl, phenyl or alkyl ester;
n is 0 to 1000;
m is 1 to 100; and
X has the following structure of formula (Ia):

where
R 10 is OH, O-alkyl, O-allyl, O-phenyl or an alkyl ester;
R 11 , R 12 , R 13 , R 14 , R 15 , R 16 independently of one another are H, alkyl or phenyl;
o is 0-100;
p is 1-100;
t is 0 or 2;
u is 0-10;
v is 0-10; and
w, x, y, z independently of one another are 1-10.

6. The process according to claim 1 , wherein said neutralizing iv) takes place in the presence of at least one polymerizable plasticizer monomer which is subsequently polymerized in a radical aqueous emulsion polymerization, optionally with addition of the further shell-forming monomer M5.

7. The process according to claim 6 , wherein the at least one polymerizable plasticizer monomer is selected from the group consisting of a styrene, α-methylstyrene, methyl 2-tert-butylacrylate, 2-methyl-2-butene, 2,3-dimethyl-2-butene, 1,1-diphenylethene, an ester of 2-phenylacrylic acid, and an ester of atropic acid.

8. The process according to claim 1 , further comprising
v) forming at least one further shell by radical aqueous emulsion polymerization of the shell-forming monomer M5 in the presence of the emulsion polymer particles obtained in said forming iii).

9. The process according to claim 1 , wherein the monomer M1 is selected from the group consisting of an ester of monoethylenically unsaturated C 3 -C 8 monocarboxylic acid with C 1 -C 10 alkanol, an ester of monoethylenically unsaturated C 4 -C 8 dicarboxylic acid with C 1 -C 10 alkanol and a mixture thereof.

10. The process according to claim 1 , wherein the monomer M2 is selected from the group consisting of a monoethylenically unsaturated C 3 -C 8 monocarboxylic acid, a salt and an anhydride thereof, and a mixture thereof.

11. The process according to claim 1 , wherein the monomer M3 is selected from the group consisting of an ester of monoethylenically unsaturated C 3 -C 8 monocarboxylic acid with C 10 -C 10 alkanol, an ester of monoethylenically unsaturated C 4 -C 8 dicarboxylic acid with C 1 -C 10 alkanol and a mixture thereof.

12. The process according to claim 1 , wherein the monomer M4 is selected from the group consisting of a monoethylenically unsaturated C 3 -C 8 monocarboxylic acid, a salt and an anhydride thereof, and a mixture thereof.

13. The process according to claim 1 , wherein the shell-forming monomer M5 in said forming iii) is selected from the group consisting of a nonionic ethylenically unsaturated monomer M5-1 having a water-solubility ≤50 g/L at 20° C., a mixture thereof, and an ethylenically unsaturated monomer M5-2 selected from the group consisting of a monomer M5-2a which comprises at least one anionic or anionogenic group, a neutral monomer M5-2b which have a water-solubility of >50 g/L at 20° C., and a mixture thereof.

14. The process according to claim 13 , wherein the monomers M5 comprise:
g) 25 to 100.0 wt % of at least one monomer M5-1, and
h) 0 to 75.0 wt % of at least one monomer M5-2,
based on a total weight of the monomers M5.

15. The process according to claim 13 , wherein the monomer M5 is the monomer M5-1, which is at least one selected from the group consisting of an ester of monoethylenically unsaturated C 3 -C 8 monocarboxylic acid with C 1 -C 10 alkanol, an ester of monoethylenically unsaturated C 4 -C 8 dicarboxylic acid with C 1 -C 10 alkanol, a vinylaromatic, and an ester of vinyl alcohol or allyl alcohol with aliphatic C 1 -C 10 monocarboxylic acid.

16. The process according to claim 13 , wherein the monomer M5 is the monomer M5-2, which is at least one selected from the group consisting of a monoethylenically unsaturated C 3 -C 8 monocarboxylic acid, a salt and an anhydride thereof, and an unsaturated fatty acid.

17. An aqueous polymer dispersion, obtained by the process according to claim 1 .

18. The aqueous polymer dispersion according to claim 17 , having an internal water content of 20% to 40%, based on a total water

Assignees

• Basf Se

Inventors

• Kehrloesser Daniel
• Leswin Joost
• Wiese Harm
• Steinbach Tobias

Classifications

• C08F285/00

  Macromolecular compounds obtained by polymerising monomers on to preformed graft polymers · CPC title

• C09D7/70

  characterised by shape, e.g. fibres, flakes or microspheres · CPC title

• C08F2/24 Primary

  with the aid of emulsifying agents · CPC title

• C08F220/06

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

• C09D151/003 Primary

  grafted on to macromolecular compounds obtained by reactions only involving unsaturated carbon-to-carbon bonds (C09D151/04, C09D151/06 take precedence) · CPC title