Solid polymer composition obtained by polymerization of an acid group containing monomer in the presence of a polyether compound

Patent metadata

Field	Value
Publication number	US-10323215-B2
Application number	US-201414902371-A
Country	US
Kind code	B2
Filing date	Jul 2, 2014
Priority date	Jul 3, 2013
Publication date	Jun 18, 2019
Grant date	Jun 18, 2019

Abstract

The present invention relates to a process for preparing a polymer composition, in which an α,β-ethylenically unsaturated carboxylic acid is subjected to a free-radical polymerization in the presence of at least one polyether component, to the polymer composition obtainable by this process and to the use thereof.

First claim

The invention claimed is:

1. A process for preparing a polymer composition, comprising
a) providing a monomer composition M) comprising
A) at least one α,β-ethylenically unsaturated carboxylic acid, and
B) less than 0.1% by weight, based on the total weight of the monomer composition M), of crosslinking monomers having two or more polymerizable α,β-ethylenically unsaturated double bonds per molecule,
where component A) is optionally partly replaced by C) at least one unsaturated sulfonic acid or unsaturated phosphonic acid,

b) subjecting the monomer composition M) provided in step a) to a free-radical polymerization in the presence of at least one polyether component PE), which does not have any copolymerizable double bonds, selected from the group consisting of polyetherols having a number-average molecular weight of at least 200 g/mol and the mono- and di-(C 1 -C 6 -alkyl) ethers thereof, surfactants containing polyether groups and mixtures thereof.

2. The process according to claim 1 , further comprising
c) Converting the polymer obtained in step b) to a film, to a solid coating on a substrate or to particles.

3. The process according to claim 1 , wherein the polyether component PE) comprises a polyetherol having repeat propylene oxide units or a mono- or di-(C 1 -C 6 -alkyl ether) of a polyetherol having repeat propylene oxide units, and the proportion of these repeat propylene oxide units averages not more than 18 units per molecule.

4. The process according to claim 1 , wherein the free-radical polymerization in step b) is additionally effected in the presence of a solvent S) selected from the group consisting of water, C 1 -C 6 -alkanols, polyols other than PE), the mono- and dialkyl ethers thereof, and mixtures thereof.

5. The process according claim 1 , wherein the α,β-ethylenically unsaturated carboxylic acid A) is selected from the group consisting of acrylic acid, methacrylic acid, ethacrylic acid, α-chloroacrylic acid, crotonic acid, maleic acid, itaconic acid, citraconic acid, mesaconic acid, glutaconic acid, aconitic acid, fumaric acid and mixtures thereof.

6. The process according to claim 1 , wherein the monomer composition M) further comprises, as component C), at least one unsaturated sulfonic acid or unsaturated phosphonic acid.

7. The process according to claim 1 , wherein the monomer composition M) comprises at least 80% by weight, based on the total weight of the monomer composition M), of at least one α,β-ethylenically unsaturated acid selected from the group consisting of acrylic acid, methacrylic acid, 2-acrylamido-2-methylpropanesulfonic acid and mixtures thereof.

8. The process according to claim 1 , wherein the monomer composition M) comprises at least 80% by weight, based on the total weight of the monomer composition M), of acrylic acid.

9. The process according to claim 1 , wherein the monomer composition M) further comprises at least one monomer D) selected from the group consisting of compounds of the general formulae (I.a) and (I.b)

wherein
the sequence of the alkylene oxide units is arbitrary,
k and l are each independently an integer from 0 to 1000, where the sum of k and l is at least 2,
R 1 is hydrogen or C 1 -C 8 -alkyl,
R 2 is hydrogen, C 1 -C 30 -alkyl, C 2 -C 30 -alkenyl or C 5 -C 8 -cycloalkyl,
X is O or a group of the formula NR 3 in which R 3 is H, alkyl, alkenyl, cycloalkyl, heterocycloalkyl, aryl or hetaryl.

10. The process according to claim 1 , wherein the monomer composition M) further comprises at least one comonomer selected from the group consisting of
E) vinylaromatics,
F) C 2 -C 8 monoolefins, nonaromatic hydrocarbons having at least two conjugated double bonds,
G) esters of α,β-ethylenically unsaturated mono- and dicarboxylic acids with C 1 -C 30 -alkanols,
H) compounds having one free-radically polymerizable α,β-ethylenically unsaturated double bond and at least one cationogenic and/or cationic group per molecule,
I) esters of vinyl alcohol or allyl alcohol with C 1 -C 30 -monocarboxylic acids,
K) monomers containing amide groups,
L) esters of α,β-ethylenically unsaturated mono- and dicarboxylic acids with C 2 -C 30 -alkanediols, amides of α,β-ethylenically unsaturated mono- and dicarboxylic acids with C 2 -C 30 -amino alcohols having a primary or secondary amino group,
M) α,β-ethylenically unsaturated nitriles,
N) vinyl halides, vinylidene halides,
O) monomers having urea groups,
and mixtures thereof.

11. The process according to claim 1 , wherein the monomer composition M) comprises acrylic acid and at least one comonomer selected from the group consisting of α,β-ethylenically unsaturated carboxylic acids other than acrylic acid and derivatives thereof, C 2 -C 10 -monoolefins, nonaromatic hydrocarbons having at least two conjugated double bonds, vinylaromatics, N-vinyllactams and mixtures thereof.

12. The process according to claim 1 , wherein the polyether component PE) comprises at least one polyetherol having a number-average molecular weight in the range from about 200 to 100 000 g/mol or a mono- or di-(C 1 -C 2 -alkyl ether) thereof.

13. The process according to claim 1 , wherein the polyether component PE) comprises at least one polyetherol or a mono- or di-(C 1 -C 2 -alkyl ether) thereof comprising exclusively ethylene oxide units as alkylene oxide units.

14. The process according to claim 1 , wherein the polyether component PE) comprises at least one surfactant containing polyether groups, selected from the group consisting of alkyl polyoxyalkylene ethers, aryl polyoxyalkylene ethers, alkylaryl polyoxyalkylene ethers, alkoxylated animal and/or vegetable fats and/or oils, fatty amine alkoxylates, fatty acid amide alkoxylates, fatty acid diethanolamide alkoxylates, polyoxyethylene sorbitan fatty acid esters, alkyl polyether sulfates, aryl polyether sulfates, alkylaryl polyether sulfates, alkyl polyether sulfonates, aryl polyether sulfonates, alkylaryl polyether sulfonates, alkyl polyether phosphates, aryl polyether phosphates, alkylaryl polyether phosphates, glyceryl ether sulfonates, glyceryl ether sulfates, monoglyceride (ether) sulfates, fatty acid amide ether sulfates, polyoxyalkylene sorbitan fatty acid esters, and mixtures thereof.

15. The process according to claim 1 , wherein the polyether component PE) comprises at least one surfactant containing polyether groups, selected from the group consisting of:
alkyl polyoxyalkylene ethers of the general formula (VI)
R 10 —O—(CH 2 CH 2 O) x —(CHR 11 CH 2 O) y —R 12

wherein R 10 is a linear or branched alkyl radical having 8 to 22 carbon atoms,
R 11 and R 12 are each independently hydrogen or a linear or branched alkyl radical having 1-10 carbon atoms or H, and
x and y are each independently 0 to 300, where the sum of x and y is >0;
surfactants containing hydroxyl groups of the general formula (VII)
R 13 —O—(CH 2 CH 2 O) s —(CH 2 CH 2 CH 2 O) t —(CH 2 CH 2 CH 2 CH 2 O) u —(CH 2 CHR 14 O) v —CH 2 CH(OH)R 15

where
the sequence of the alkylene oxide units in the compounds of the formula (VII) is arbitrary,
s, t, u and v are each independently an integer from 0 to 500, where the sum of s, t, u and v is >0,
R 13 and R 15 are each independently a straight-chain or branched saturated C 1 -C 40 -alkyl radical or a mono- or polyunsaturated C 2 -C 40 -alkenyl radical, and
R 14 is methyl, ethyl, n-propyl, isopropyl or n-butyl;
fatty alcohol polyoxyalkylene esters of the general formula (VIII)
R

Assignees

• Basf Se

Inventors

• Fuchs Yannick
• Witteler Helmut
• Weber Heike
• Garcia Marcos Alejandra
• Detering Jürgen

Classifications

• C08F283/06 Primary

  on to polyethers, polyoxymethylenes or polyacetals {(C08F283/004 takes precedence)} · CPC title

• C08F2/24 Primary

  with the aid of emulsifying agents · CPC title

• C09J133/02

  Homopolymers or copolymers of acids; Metal or ammonium salts thereof · CPC title

• C11D3/3757 Primary

  (Co)polymerised carboxylic acids, -anhydrides, -esters in solid and liquid compositions · CPC title

• C11D17/003

  Colloidal solutions, e.g. gels; Thixotropic solutions or pastes · CPC title