IP Library Granted Patent US 9,315,943
Granted Patent B2
US 9,315,943 · App. 14/350,467 · Granted Apr 19, 2016

Finely divided, starch-containing polymer dispersions, processes for their preparation and use as sizes in papermaking

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Quick Facts
Patent No.
US 9,315,943
App. No.
14/350,467
Granted
Apr 19, 2016
Kind
B2
Abstract

A finely divided, starch-containing polymer dispersion which is obtainable by free radical emulsion polymerization of ethylenically unsaturated monomers in the presence of at least one redox initiator and starch, wherein (a) from 0 to less than 40% by weight of at least one optionally substituted styrene, (b) from greater than 60 to 100% by weight of at least one C 1 -C 12 -alkyl acrylate and/or C 1 -C 12 -alkyl methacrylate, (c) from 0 to 10% by weight of at least one other ethylenically unsaturated copolymerizable monomer, are used as the ethylenically unsaturated monomers, the sum (a)+(b)+(c) being 100% and being based on the active monomer content and (d) from 15 to 40% by weight of at least one degraded starch which has a molar mass M w of from 1000 to 65 000 g/mol, based on the total weight of solids content of components (a)+(b)+(c)+(d), are used as the starch, and the polymerization being carried out in the presence of at least 0.01% by weight, based on the monomers used, of at least one terpene containing chain-transfer agent, and in which the polymer dispersion optionally comprises an aluminum compound. The use of the finely divided, starch-containing polymer dispersions as sizes for paper, board and cardboard is also claimed.

Claims (24)

1. A finely divided, starch-containing polymer dispersion obtained by a process comprising: free radical emulsion polymerization of ethylenically unsaturated monomers in the presence of at least one redox initiator and at least one starch, wherein the ethylenically unsaturated monomers comprise:

(a) 20 to 35% by weight of at least one optionally substituted styrene;

(b) 65 to 75% by weight of at least one C 1 -C 4 -alkyl acrylate; and

(c) 0 to 5% by weight of at least one other ethylenically unsaturated copolymerizable monomer;

wherein the sum (a)+(b)+(c) is 100% based on active monomer content and the starch comprises:

(d) 25 to 35% by weight of at least one degraded anionic starch which has a molar mass M w of from 2500 to 35 000 g/mol, based on the total weight of solids content of components (a)+(b)+(c)+(d); and

the polymerization is carried out in the presence of at least one terpene-containing chain-transfer agent of at least 0.01% by weight, based on the monomers used and

the polymer dispersion may comprise 0.1 to 50% of an aluminium compound based on the total weight of the solids content of the polymer dispersion.

2. The finely divided, starch-containing polymer dispersion of claim 1 , wherein the terpene-containing chain-transfer agent is used in an amount of 0.01 to 10% by weight, based on the monomers.

3. The finely divided, starch-containing polymer dispersion of claim 1 , wherein the terpene-containing chain-transfer agent is used in an amount of 0.05 to 5% by weight, based on the monomers.

4. The finely divided, starch-containing polymer dispersion of claim 1 , wherein the chain-transfer agent is a monocyclic monoterpene; and

wherein the monocyclic monoterpene is terpinolene.

5. The finely divided, starch-containing polymer dispersion of claim 1 , wherein the polymerization is carried out in the presence of 0.05 to 5% by weight of terpinolene as the chain-transfer agent.

6. A process for the preparation of the finely-divided, starch-containing polymer dispersion of claim 1 , comprising

polymerizing the ethylenically unsaturated monomers in the presence of a redox initiator in an aqueous medium.

7. The process of claim 6 , wherein the chain-transfer agent is a monocyclic monoterpene; and

wherein the monocyclic monoterpene is terpinolene.

8. The process of claim 6 , wherein the polymerization is carried out in the presence of from 0.05 to 5% by weight of at least one terpene-containing chain-transfer agent.

9. The process of claim 8 , wherein the polymerization is carried out in the presence of from 0.05 to 5% by weight of terpinolene as the chain-transfer agent.

10. The process of claim 6 , further comprising:

adding to the polymer dispersion after polymerization an initiator selected from the group consisting of hydrogen peroxide, peroxides, hydroperoxides and azo initiators; and

postpolymerizing the polymer dispersion.

11. The process of claim 10 , further comprising:

adding tert-butyl hydroperoxide to the polymer dispersion during postpolymerization.

Assignments (12)
SECURITY INTEREST Recorded Nov 14, 2025
From: CHEM-AQUA, INC.; DIVERSEY, INC.; DIVERSEY TASKI, INC.; INNOVATIVE WATER CARE, LLC; NCH CORPORATION; NCH LIFE SCIENCES LLC; SOLENIS TECHNOLOGIES, L.P.
To: THE BANK OF NEW YORK MELLON TRUST COMPANY, N.A., AS NOTES COLLATERAL AGENT
Reel/Frame 073570/0838 →
RELEASE OF SECURITY INTEREST Recorded Nov 14, 2025
From: THE BANK OF NEW YORK MELLON TRUST COMPANY, N.A., AS NOTES COLLATERAL AGENT
To: BIRKO CORPORATION; DIVERSEY, INC.; DIVERSEY TASKI, INC.; INNOVATIVE WATER CARE, LLC; SOLENIS TECHNOLOGIES, L.P.
Reel/Frame 073564/0864 →
SECURITY AGREEMENT (NOTES) Recorded Oct 10, 2025
From: DIVERSEY, INC.; DIVERSEY TASKI, INC.; INNOVATIVE WATER CARE, LLC; SOLENIS TECHNOLOGIES, L.P.
To: THE BANK OF NEW YORK MELLON TRUST COMPANY, N.A., AS NOTES COLLATERAL AGENT
Reel/Frame 073061/0885 →
RELEASE OF 2023 NOTES PATENT SECURITY INTERESTS Recorded Oct 10, 2025
From: THE BANK OF NEW YORK MELLON TRUST COMPANY, N.A.
To: BIRKO CORPORATION; DIVERSEY, INC.; DIVERSEY TASKI, INC.; INNOVATIVE WATER CARE, LLC; SOLENIS TECHNOLOGIES, L.P.
Reel/Frame 073074/0198 →
SECURITY AGREEMENT (2024 NOTES) Recorded Jun 24, 2024
From: BIRKO CORPORATION; DIVERSEY, INC.; DIVERSEY TASKI, INC.; INNOVATIVE WATER CARE, LLC; SOLENIS TECHNOLOGIES, L.P.
To: THE BANK OF NEW YORK MELLON TRUST COMPANY, N.A., AS NOTES COLLATERAL AGENT
Reel/Frame 067824/0278 →
2023 NOTES PATENT SECURITY AGREEMENT Recorded Jul 7, 2023
From: BIRKO CORPORATION; SOLENIS TECHNOLOGIES, L.P.; INNOVATIVE WATER CARE, LLC; DIVERSEY, INC.; DIVERSEY TASKI, INC.; INNOVATIVE WATER CARE GLOBAL CORPORATION
To: BANK OF NEW YORK MELLON TRUST COMPANY, N.A.
Reel/Frame 064225/0170 →
SECURITY AGREEMENT (NOTES) Recorded Sep 14, 2022
From: SOLENIS TECHNOLOGIES, L.P.; INNOVATIVE WATER CARE, LLC
To: THE BANK OF NEW YORK MELLON TRUST COMPANY, N.A. AS COLLATERAL AGENT
Reel/Frame 061432/0821 →
NOTES SECURITY AGREEMENT Recorded Nov 10, 2021
From: INNOVATIVE WATER CARE, LLC; SOLENIS TECHNOLOGIES, L.P.
To: THE BANK OF NEW YORK MELLON TRUST COMPANY, N.A.
Reel/Frame 058103/0066 →
TERM LOAN PATENT SECURITY AGREEMENT Recorded Nov 10, 2021
From: INNOVATIVE WATER CARE, LLC; SOLENIS TECHNOLOGIES, L.P.
To: GOLDMAN SACHS BANK USA
Reel/Frame 058102/0407 →
ABL PATENT SECURITY AGREEMENT Recorded Nov 10, 2021
From: INNOVATIVE WATER CARE, LLC; SOLENIS TECHNOLOGIES, L.P.
To: BANK OF AMERICA, N.A.
Reel/Frame 058102/0122 →
ASSIGNMENT OF ASSIGNOR'S INTEREST Recorded Dec 23, 2020
From: BASF SE
To: SOLENIS TECHNOLOGIES, L.P.
Reel/Frame 054735/0659 →
ASSIGNMENT OF ASSIGNOR'S INTEREST Recorded Apr 8, 2014
From: CIMPEANU, CARMEN-ELENA; KERN, HOLGER; ARNOLD, PETRA; HAMERS, CHRISTOPH
To: BASF SE
Reel/Frame 032627/0425 →