Carboxyl-group-containing copolymer, and method for producing same

Patent metadata

Field	Value
Publication number	US-11021557-B2
Application number	US-201716464182-A
Country	US
Kind code	B2
Filing date	Nov 22, 2017
Priority date	Nov 28, 2016
Publication date	Jun 1, 2021
Grant date	Jun 1, 2021

Abstract

The present invention provides a carboxyl group-containing copolymer having a better calcium ion trapping ability and a better carbon black dispersing ability than any conventional carboxyl group-containing copolymers. The present invention relates to a carboxyl group-containing copolymer including a structural unit (a) derived from an unsaturated monocarboxylic acid monomer (A), a structural unit (b) derived from an unsaturated dicarboxylic acid monomer (B), and a structural unit (c) derived from a cationic monomer (C).

First claim

The invention claimed is:

1. A carboxyl group-containing copolymer comprising:
a structural unit (a) derived from an unsaturated monocarboxylic acid monomer (A),
a structural unit (b) derived from an unsaturated dicarboxylic acid monomer (B), and
a structural unit (c) derived from a cationic monomer (C),
wherein the carboxyl group-containing copolymer optionally contains at least one selected from the group consisting of a structural unit (d) derived from a sulfonic acid group-containing monomer (D), and a structural unit (e) derived from a monomer (E) other than the unsaturated monocarboxylic acid monomer (A), the unsaturated dicarboxylic acid monomer (B), the cationic monomer (C), and the sulfonic acid group-containing monomer (D),
a proportion of the structural unit (b) in 100 mol % of all structural units is 10 to 70 mol %,
a proportion of the structural unit (e) in 100 mol % of all structural units is 0 to 20 mol %,
wherein the cationic monomer (C) contains a group represented by any of the following formulas (1) to (3):

wherein in the formulas (1) and (2), R 1 and R 2 are the same as or different from each other and each represents a hydrogen atom or a C1-C20 hydrocarbon group optionally containing a functional group, at least one of R 1 or R 2 being a C1-C20 hydrocarbon group optionally containing a functional group,
in the formula (3), R 3 to R 5 are the same as or different from each other and each represent a C1-C20 hydrocarbon group optionally containing a functional group, and
W − is an anion.

2. The carboxyl group-containing copolymer according to claim 1 , further comprising the structural unit (d) derived from a sulfonic acid group-containing monomer (D).

3. The carboxyl group-containing copolymer according to claim 1 ,
wherein the cationic monomer (C) contains a hydrophobic group.

4. The carboxyl group-containing copolymer according to claim 1 ,
wherein the unsaturated monocarboxylic acid monomer (A) includes at least one selected from the group consisting of (meth)acrylic acid and salts of (meth)acrylic acid.

5. The carboxyl group-containing copolymer according to claim 1 ,
wherein the unsaturated dicarboxylic acid monomer (B) includes at least one selected from the group consisting of maleic acid, salts of maleic acid, and maleic anhydride.

6. The carboxyl group-containing copolymer according to claim 1 ,
wherein the carboxyl group-containing copolymer has a weight average molecular weight of 2000 to 500000.

7. A scale inhibitor comprising the carboxyl group-containing copolymer according to claim 1 .

8. A method for producing a carboxyl group-containing copolymer, the method comprising polymerizing a monomer component that contains an unsaturated dicarboxylic acid monomer (B) and a hydrophobic group-containing cationic monomer (C1),
wherein the monomer component optionally contains at least one selected from the group consisting of an unsaturated monocarboxylic acid monomer (A), a sulfonic acid group-containing monomer (D), and a monomer (E) other than the unsaturated monocarboxylic acid monomer (A), the unsaturated dicarboxylic acid monomer (B), the hydrophobic group-containing cationic monomer (C1), and the sulfonic acid group-containing monomer (D),
a proportion of the unsaturated dicarboxylic acid monomer (B) in 100 mol % of all monomers of the monomer component is 10 to 70 mol %,
a proportion of the monomer (E) in 100 mol % of all monomers is 0 to 20 mol %,
wherein polymerization is conducted at a pH of 0 to 6 for at least 30% of a time, taking, from a start of the polymerization reaction to an end of a last completed addition of addition of a monomer component, addition of a chain transfer agent, and addition of a polymerization initiator, as 100%,
wherein the hydrophobic group-containing cationic monomer (C1) contains a group represented by any of the following formulas (6) to (8):

wherein in the formulas (6) and (7), R 11 and R 12 are the same as or different from each other and each represents a hydrogen atom or a C1-C20 hydrocarbon group optionally containing a functional group, at least one of R 11 or R 12 is a C1-C20 hydrocarbon group containing no functional group or containing a hydrophobic functional group, and a total carbon number of the hydrocarbon groups R 11 and R 12 is 4 or more,
in the formula (8), R 13 to R 15 are the same as or different from each other and each represent a C1-C20 hydrocarbon group optionally containing a functional group, at least one of R 13 to R 15 being a C1-C20 hydrocarbon group containing no functional group or containing a hydrophobic functional group,
and in the formulas (7) and (8), W − is an anion.

9. The method for producing a carboxyl group-containing copolymer according to claim 8 ,
wherein the unsaturated dicarboxylic acid monomer (B) includes at least one selected from the group consisting of maleic acid, salts of maleic acid, and maleic anhydride.

10. The method for producing a carboxyl group-containing copolymer according to claim 8 ,
wherein the monomer component contains an unsaturated monocarboxylic acid monomer (A).

11. The method for producing a carboxyl group-containing copolymer according to claim 8 ,
wherein the polymerization is conducted at 70° C. to 120° C.

12. The method for producing a carboxyl group-containing copolymer according to claim 8 ,
wherein the carboxyl group-containing copolymer has a weight average molecular weight of 2000 to 500000.

13. The method for producing a carboxyl group-containing copolymer according to claim 8 ,
wherein an amount of the chain transfer agent is 1 to 20 g relative to 1 mol total of the monomer component.

14. The method for producing a carboxyl group-containing copolymer according to claim 8 , wherein a number of carbon atoms of the hydrocarbon group in R 11 -R 15 is from 2 to 20 each.

15. The method for producing a carboxyl group-containing copolymer according to claim 8 , wherein the cationic monomer (C1) is represented by the formula (9).

16. The method for producing a carboxyl group-containing copolymer according to claim 8 , wherein R 11 and R 12 are the same as or different from each other and each represents a C1-C20 hydrocarbon group optionally containing a functional group.

17. The method for producing a carboxyl group-containing copolymer according to claim 8 , wherein the upper limit of pH in the polymerizing is 5.8.

Assignees

• Nippon Catalytic Chem Ind

Inventors

• Takahashi Hikaru
• Takechi Ryosuke
• Ono Yasuhiro

Classifications

• C11D3/3757

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

• C08F222/02

  Acids; Metal salts or ammonium salts thereof {, e.g. maleic acid or itaconic acid} · CPC title

• C08F222/06

  Maleic anhydride · CPC title

• C08F226/00

  Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a single or double bond to nitrogen or by a heterocyclic ring containing nitrogen · CPC title

• C11D3/0036 Primary

  Soil deposition preventing compositions; Antiredeposition agents · CPC title