IP Library Granted Patent US 9,321,851
Granted Patent B2
US 9,321,851 · App. 13/412,075 · Granted Apr 26, 2016

Water soluble polymer powder formulation having improved dispersing properties

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Quick Facts
Patent No.
US 9,321,851
App. No.
13/412,075
Granted
Apr 26, 2016
Kind
B2
Abstract

The present invention relates generally to water soluble polymer powder formulations, and more particularly, to a cellulose ether formulation which in powder form is suitable for direct addition to water-based systems to produce smooth, lump free solutions. The cellulose ethers are crosslinked with an aldehyde crosslinker and include a dry weak acid which slows hydrolysis of the hermiacetal linkage formed by the crosslinker. The selected acid does not adversely affect solubility stability.

Claims (24)

1. A storage stable cellulose ether formulation which disperses in water without forming lumps, comprising:

a) a cellulose ether at least partially crosslinked with a crosslinker having a first reactive moiety and a second reactive moiety, wherein said first reactive moiety is an aldehyde and said second reactive moiety is selected from the group consisting of aldehyde, silanol, isocyanate, halomethyl, alkyl tosylate ether, epoxide, and combinations thereof; and

b) a solid water soluble acid selected from the group consisting of amino acids, partially neutralized polycarboxylic acids, and combinations thereof, wherein said solid water soluble acid has a pKa of 4.2 to 6 and is present in the storage stable cellulose ether formulation in a range of from more than 1 to about 20 wt % of the formulation.

2. The formulation of claim 1 , wherein said cellulose ether is selected from the group consisting of hydroxyethyl cellulose (HEC), hydroxypropyl cellulose (HPC), water soluble ethylhydroxyethyl cellulose (EHEC), carboxymethyl cellulose (CMC), carboxymethylhydroxyethyl cellulose (CMHEC), hydroxypropylhydroxyethyl cellulose (HPHEC), methylcellulose (MC), methylhydroxypropyl cellulose (MHPC), methylhydroxyethyl cellulose (MHEC), carboxymethylmethylcellulose (CMMC), hydrophobically modified carboxymethylcellulose (HMCMC), hydrophobically modified hydroxyethyl cellulose (HMHEC), hydrophobically modified hydroxypropyl cellulose (HMHPC), hydrophobically modified ethylhydroxyethyl cellulose (H M EH EC), hydrophobically modified carboxymethylhydroxyethyl cellulose (HMCMHEC), hydrophobically modified hydroxypropylhydroxy ethyl cellulose (HMHPHEC), hydrophobically modified methyl cellulose (HMMC), hydrophobically modified methylhydroxypropyl cellulose (HMMHPC), hydrophobically modified methylhydroxyethyl cellulose (HMMHEC), hydrophobically modified carboxymethylmethyl cellulose (HMCMMC), cationic hydroxyethyl cellulose (cationic HEC) and cationic hydrophobically modified hydroxyethyl cellulose (cationic HMHEC).

3. The formulation of claim 1 , wherein said partially neutralized polycarboxylic acid is selected from the group consisting of adipic acid, aldaric acid, citric acid, isocitric acid, tartaric acid, oxalic acid, malonic acid, maleic acid, itaconic acid, succinic acid, glutaric acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, phathalic acid, aconitic acid, propane- 1,2,3 tricarboxylic acid, trimethic acid, polyacrylic acid, polymethacrylic acid, and combinations thereof.

4. The formulation of claim 3 , wherein said partially neutralized polycarboxylic acid is partially neutralized citric acid.

5. The formulation of claim 1 containing from about 0.01to about 8 weight percent of said crosslinker.

6. The formulation of claim 5 containing from about 0.01 to 5weight percent of said crosslinker.

7. The formulation of claim 1 comprising 50 to 99 weight percent of said crosslinked cellulose ether.

8. The formulation of claim 1 , wherein said crosslinker comprises glyoxal.

9. The formulation of claim 1 , wherein said partially neutralized polycarboxylic acid is capable of providing said crosslinked cellulose ether solubility stability after being stored at a temperature of 60° C. for at least 3 days.

10. The formulation of claim 1 , wherein said partially neutralized polycarboxylic acid is capable of providing said crosslinked cellulose ether solubility stability after being stored at a temperature of 60° C. for at least 10 days.

11. The formulation of claim 1 , wherein solid water soluble acid is monosodium citrate.

12. A method of thickening a water-based system comprising, adding a desired amount of a dry blend to a water-based system, said dry blend comprising:

(a) 50 to about 99 weight percent of an at least partially crosslinked cellulose ether comprising 0.01 to about 8 weight percent of a crosslinker having a first reactive moiety and a second reactive moiety, wherein said first reactive moiety is an aldehyde and said second reactive moiety is selected from the group consisting of aldehyde, silanol, isocyanate, halomethyl, alkyl tosylate ether, epoxide, and combinations thereof; and

(b) from more than 1 to about 20 weight percent of an acid selected from the group consisting of partially neutralized polycarboxylic acids, amino acids, and combinations thereof, wherein said acid has a pKa of 4.2 to 6.

13. The method of claim 12 , wherein said crosslinker is glyoxal.

14. The method of claim 12 , wherein said water-based system is a paint.

15. The method of claim 14 , wherein said dry blend is added to a pigment grind.

16. The method of claim 12 , wherein the acid is monosodium citrate.

17. A storage stable cellulose ether formulation which disperses in water without forming lumps comprising:

a) an at least partially crosslinked cellulose ether, wherein said at least partially crosslinked cellulose ether comprises a crosslinker having a first reactive moiety and a second reactive moiety, wherein said first reactive moiety is an aldehyde and said second reactive moiety is selected from the group consisting of aldehyde, silanol, isocyanate, halomethyl, alkyl tosylate ether, epoxide, and combinations thereof; and

b) a partially neutralized polycarboxylic acid selected from the group consisting of adipic acid, aldaric acid, citric acid, isocitric acid, tartaric acid, oxalic acid, malonic acid, maleic acid, itaconic acid, succinic acid, glutaric acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, phathalic acid, aconitic acid, propane- 1,2,3 tricarboxylic acid, trimethic acid, and combinations thereof, wherein said partially neutralized polycarboxylic acid is present in the storage stable cellulose ether formulation in a range of from more than 1 to about 20 wt % of the formulation.

18. The formulation of claim 17 , wherein the partially neutralized polycarboxylic acid is monosodium citrate.

Assignments (7)
RELEASE OF SECURITY INTEREST Recorded Jan 10, 2020
From: THE BANK OF NOVA SCOTIA
To: AVOCA LLC; HERCULES LLC; ISP INVESTMENTS LLC; PHARMACHEM LABORATORIES LLC
Reel/Frame 051557/0504 →
SECURITY AGREEMENT Recorded Jul 3, 2017
From: AVOCA, INC.; HERCULES LLC; ISP INVESTMENTS LLC; PHARMACHEM LABORATORIES, INC.
To: THE BANK OF NOVA SCOTIA, AS ADMINISTRATIVE AGENT
Reel/Frame 043084/0753 →
CHANGE OF NAME Recorded May 18, 2017
From: HERCULES INCORPORATED
To: HERCULES LLC
Reel/Frame 042497/0331 →
CORRECTIVE ASSIGNMENT TO CORRECT THE CONVEYING PARTY DATA: DELETE GLENN T CARROLL PREVIOUSLY RECORDED ON REEL 028406 FRAME 0354. ASSIGNOR(S) HEREBY CONFIRMS THE ASSIGMENT. Recorded Sep 13, 2013
From: BHARGAVA, PRACHUR; NGUYEN, TUYEN T.; VAYNBERG, KONSTANTIN A.
To: HERCULES INCORPORATED
Reel/Frame 031289/0766 →
RELEASE OF PATENT SECURITY AGREEMENT Recorded Mar 18, 2013
From: THE BANK OF NOVA SCOTIA
To: ASHLAND LICENSING AND INTELLECTUAL PROPERTY LLC; AQUALON COMPANY; ISP INVESTMENTS INC.; HERCULES INCORPORATED
Reel/Frame 030025/0320 →
ASSIGNMENT OF ASSIGNOR'S INTEREST Recorded Jun 19, 2012
From: BHARGAVA, PRACHUR; CARROLL, GLENN T.; NGUYEN, TUYEN T.; VAYNBERG, KONSTANTIN A.
To: HERCULES INCORPORATED
Reel/Frame 028406/0354 →
SECURITY AGREEMENT Recorded Apr 4, 2012
From: HERCULES INCORPORATED; ISP INVESTMENTS INC.
To: THE BANK OF NOVA SCOTIA
Reel/Frame 027991/0859 →