Polyacrylic acid (salt), polyacrylic acid (salt)-based water-absorbing resin, and process for producing same

• US 10,640,588 B2
• Filed: 02/23/2017
• Issued: 05/05/2020
• Est. Priority Date: 04/26/2010
• Status: Active Grant

• Current Assignee: Nippon Shokubai Company Limited
• Original Assignee: Nippon Shokubai Company Limited
• Inventors: Matsumoto, Satoshi, Kabeya, Yuki, Ishizaki, Kunihiko, Sakamoto, Shigeru
• Primary Examiner(s): Choi, Ling Siu
• Assistant Examiner(s): Miller, David L
• Application Number:
  US15/440,817
• Publication Number:
  US 20170158791A1
• Time in Patent Office: 1,167 Days
• CPC Class Codes: B01J 20/261 obtained by reactions only involving carbon to carbon unsaturated bonds macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds per se C08F
• CPC Class Codes: B01J 20/267 Cross-linked polymers
• CPC Class Codes: B01J 20/3085 Chemical treatments not covered by groups B01J20/3007 - B01J20/3078
• CPC Class Codes: C08F 120/06 Acrylic acid; Methacrylic acid; Metal salts or ammonium salts thereof
• CPC Class Codes: C08F 20/06 Acrylic acid; Methacrylic acid; Metal salts or ammonium salts thereof
• CPC Class Codes: C08F 220/06 Acrylic acid; Methacrylic acid; Metal salts or ammonium salts thereof

Abstract

Disclosed are a polyacrylate (salt) and a polyacrylate (salt) water-absorbent resin containing a tracer which can be verified back to the manufacturing process of the water-absorbent resin when dealing with various problems with the water-absorbent resin which can occur from the manufacturing process of the water-resistant resin, during the use thereof by a consumer, up until the disposal thereof. The disclosed polyacrylate (salt) and the polyacrylate (salt) water-absorbent resin have a carbon stable isotope ratio (δ¹³C) of at least −20‰ when measured by accelerator mass spectrometry.

Claims

1. A method for producing a polyacrylic acid (salt) water-absorbing resin comprising a polymerization step for a water-soluble unsaturated monomer, a drying step for a water-containing crosslinked polymer obtained by the polymerization step to obtain a dried polymer, a pulverization step of the dried polymer, a particle size classification step of the pulverized dried polymer to obtain a classified water-absorbing resin, and a surface-crosslinking step of the classified water-absorbing resin, wherein the polyacrylic acid (salt) water-absorbing resin is a polymer containing acrylic acid and/or its salt as a repeating unit in an amount of 50 to 100 mol %;

the polymerization step is for polymerizing acrylic acid with a carbon stable isotope ratio (VC) of −

20% or higher as the water-soluble unsaturated monomer, where the acrylic acid contains an acrylic acid raw material tracer of an acrylic acid produced from a C3 plant and an acrylic acid produced from a C4 plant, wherein the amount of the acrylic acid produced from the C4 plant is 50 wt % or more based on the total amount of the acrylic acid raw material produced from the C3 plant and the C4 plant, and the amount of acrylic acid produced from the C3 plant and acrylic acid produced from the C4 plant is 50% to 99% based on the total amount of acrylic acid;

the water-soluble unsaturated monomer contains p-methoxyphenol as a polymerization inhibitor in an amount of more than 0 ppm and 200 ppm or less,

wherein a drying temperature in the drying step is 165°

C. to 230°

C., a drying time at the drying step is 10 minutes or more, and a hot air velocity in the drying step is 0.1 to 5 m/s to remove at least a portion of propionic acid from said water-absorbing resin,

said water-absorbing resin to be processed by the surface-crosslinking step contains fine particles which pass through a sieve with mesh size of 150 μ

m in an amount of 0 to 5 weight % relative to the entire water-absorbing resin and particles which do not pass through a sieve with mesh size of 850 μ

m in an amount of 0 to 5 weight % relative to the entire water-absorbing resin,

the polyacrylic acid (salt) water-absorbing resin contains p-methoxyphenol, as a polymerization inhibitor, in an amount of 1 to 160 ppm,

95 weight % or more of the polyacrylic acid (salt) water-absorbing resin has a particle size in the range of 150 to 850 μ

m relative to the polyacrylic acid (salt) water-absorbing resin,

wherein an amount of propionic acid contained in the polyacrylic acid (salt) water-absorbing resin is 1500 ppm or less, and

a carbon stable isotope ratio (δ

¹³C) of the polyacrylic acid (salt) water-absorbing resin is from −

20‰

to −

5‰

.

2. The method for producing a polyacrylic acid (salt) water-absorbing resin according to claim 1, wherein more than 50 weight % of a carbon source of the acrylic acid is obtained from biomass derived from a C4 plant.

3. The method for producing a polyacrylic acid (salt) water-absorbing resin according to claim 1, wherein the water-soluble unsaturated monomer is obtained by mixing acrylic acid having different carbon stable isotope ratios (δ

¹³C).

4. The method for producing a polyacrylic acid (salt) water-absorbing resin according to claim 1, wherein the dried material obtained in the drying step is surface-crosslinked with an organic surface-crosslinking agent after the drying step and coated with a surface treatment agent selected from a polyvalent metal salt, a polyamine polymer, and water-insoluble inorganic particles after the drying step.

5. The method for producing a polyacrylic acid (salt) water-absorbing resin according to claim 1, wherein the water-soluble unsaturated monomer further satisfies one or more of the following:

the p-methoxyphenol is used as a polymerization inhibitor and the content thereof is 1 to 160 ppm;

the content of Fe is 0 to 2 ppm; and

the content of mono- or di-hydroxyacetone is 0 to 10 ppm.

6. The method for producing a polyacrylic acid (salt) water-absorbing resin according to claim 1, wherein a fine powder recycle step is employed in addition to the above steps.

7. The method for producing a polyacrylic acid (salt) water-absorbing resin according to claim 1, wherein the polyacrylic acid (salt) water-absorbing resin contains p-methoxyphenol in an amount of 5 to 60 ppm.

8. The method for producing a polyacrylic acid (salt) water-absorbing resin according to claim 1, wherein the acrylic acid is refined by an aldehyde treatment agent or crystallization.

9. The method for producing a polyacrylic acid (salt) water-absorbing resin according to claim 1, wherein the acrylic acid is refined by multistage crystallization.

10. The method for producing a polyacrylic acid (salt) water-absorbing resin according to claim 4, wherein the surface treatment agent is used in an amount of 0.001 to 5 parts by mass relative to 100 parts by mass of said water-absorbing resin.

11. The method for producing a polyacrylic acid (salt) water-absorbing resin according to claim 4, wherein the water-insoluble inorganic particles used as the surface treatment agent is silicon dioxide.

12. The method for producing a polyacrylic acid (salt) water-absorbing resin according to claim 3, wherein the acrylic acid having different carbon stable isotope ratios (δ

¹³C) is obtained by using acrylic acids derived from a fossil raw material and a nonfossil raw material and the use ratio of two kinds of the acrylic acids is in the range of 1;

99 to 99;

1.