IP Library Granted Patent US 9,885,155
Granted Patent B2
US 9,885,155 · App. 14/683,906 · Granted Feb 6, 2018

Modified vinylamine containing polymers and their use in papermaking

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Quick Facts
Patent No.
US 9,885,155
App. No.
14/683,906
Granted
Feb 6, 2018
Kind
B2
Abstract

A graft copolymer composition of a vinyl monomer and a functionalized vinylamine-containing base polymer and a method of preparing the graft copolymer. It also relates to a paper product made using the composition as a papermaking additive.

Claims (26)

1. A graft copolymer composition of a vinyl monomer and a functionalized vinylamine-containing base polymer wherein the functionalized vinylamine-containing base polymer comprises randomly distributed repeating monomer units having the formula (I), (II) and (III),

wherein R is a reacted α,β-unsaturated alkyl carbonyl compound through Michael addition by vinylamine in the polymer; n, p and q are the numbers indicating mole % of the repeating units of formula (I), (II) and (III) present in the functionalized vinylamine-containing base polymer; and

wherein n is from about 5 mole % to about 98 mole %, p is from about 1 mole % to about 80 mole %, q is from about 1 mole % to about 30 mole %; wherein the mole ratio of the functionalized vinylamine-containing base polymer to the vinyl monomer in the graft polymer is in the range of from about 10:90 to about 50:50.

2. The composition of claim 1 , wherein the vinyl monomer is selected from the group consisting of acrylamide, acrylic acid, methacrylamide, methyl methacrylate, acrylonitrile, methyl acrylate, alkyl methacrylate, N-(2-methylpropanesulfonic acid)acrylamide, N-(glycolic acid)acrylamide, N-[3-(propyl)trimethylammonium chloride]acrylamide, and combinations thereof.

3. The composition according to claim 1 , wherein the graft copolymers can be used in combination with one or more additives.

4. The composition according to claim 3 , wherein the one or more additives can be a cationic amide-containing polymer.

5. The composition according to claim 4 , wherein the molar ratio of the cationic amide-containing polymer to the vinylamine-containing graft copolymer is from about 2:98 to about 40:60.

6. The composition according to claim 3 , wherein the one or more additives is selected from the group consisting of cationic, anionic, amphoteric, nonionic synthetic and natural polymers.

7. The composition according to claim 6 , wherein the anionic additive is selected from the group consisting of a copolymer containing acrylic acid, a copolymer of acrylamide and acrylic acid, and a carboxyl methyl cellulose.

8. The composition according to claim 6 , wherein the cationic additive is selected from the group consisting of crosslinked polyamidoamines, polydiallyldimethylammonium chlorides, and polyamines.

9. The composition according to claim 3 , wherein the one or more additives is selected from the group consisting of polymeric aldehyde-functional compounds.

10. The composition according to claim 9 , wherein the polymeric aldehyde-functional compound is selected from the group consisting of glyoxalated polyacrylamides, aldehyde celluloses and aldehyde functional polysaccharides.

11. The composition according to claim 1 , wherein n is from about 50% to about 98 mole %, p is from about 1 mole % to about 30 mole %, and q is from about 1 mole % to about 15 mole %, and the mole ratio of the functionalized vinylamine-containing base polymer to vinyl monomer is from about 10:90 to about 50:50.

12. The composition according to claim 1 , wherein n is from about 80% to about 98 mole %, p is from about 1 mole % to about 15 mole %, q is from about 1 mole % to about 8 mole %, and the mole ratio of the functionalized vinylamine-containing base polymer to vinyl monomer is from about 10:90 to about 50:50.

13. A method of making a graft copolymer composition comprising:

dissolving a functionalized vinylamine-containing base polymer in an aqueous media;

adjusting the pH of the aqueous media to from about 1 to about 4;

conducting free radical polymerization at a temperature of from about 30° C. to about 100° C.;

for from about 10 minutes to about 300 minutes producing a functionalized polyvinylamine graft copolymer;

wherein the functionalized vinylamine-containing base polymer comprises randomly distributed repeating monomer units having the formula (I) (II) and (III):

wherein R is a reacted α,β-unsaturated alkyl carbonyl compound; n, p and q indicate the mole percent of the repeating units of formula (I), (II) and/or (III) present in the functionalized polyvinylamine;

wherein n is from about 5 mole % to about 98 mole %, p is at least 1 mole % to about 80 mole %, q is from 01 mole % to about 30 mole %; and wherein the mole ratio of the functionalized vinylamine-containing base polymer to the vinyl monomer in the graft polymer is in the range of from about 10:90 to about 50:50.

14. The method according to claim 13 , wherein the pH of the graft polymerization is from about 2 to about 4.

15. The method according to claim 13 , further comprises adding an initiator to the polymerization reaction, wherein the initiator is selected from the group consisting of hydrogen peroxide, tert-butylhydroperoxide, persulfates, azo initiator and redox initiator systems and combinations thereof.

16. The method according to claim 15 , wherein the initiator is hydrogen peroxide.

17. The method according to claim 13 , wherein the functionalized polyvinylamines are the products of Michael addition of the base polymer and the unsaturated alkyl carbonyl compound.

Assignments (15)
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 →
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 (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 →
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 →
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 →
RELEASE OF SECURITY INTEREST Recorded Nov 10, 2021
From: CITIBANK, N.A.
To: SOLENIS TECHNOLOGIES, L.P.
Reel/Frame 058848/0636 →
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 →
RELEASE OF SECURITY INTEREST Recorded Nov 10, 2021
From: CREDIT SUISSE AG, CAYMAN ISLANDS BRANCH
To: SOLENIS TECHNOLOGIES, L.P.
Reel/Frame 058856/0724 →
FIRST LIEN NOTICE AND CONFIRMATION OF GRANT OF SECURITY INTEREST IN PATENTS Recorded Jul 20, 2018
From: SOLENIS TECHNOLOGIES, L.P.
To: CITIBANK, N.A., COLLATERAL AGENT
Reel/Frame 046595/0241 →
SECOND LIEN NOTICE AND CONFIRMATION OF GRANT OF SECURITY INTEREST IN PATENTS Recorded Jul 20, 2018
From: SOLENIS TECHNOLOGIES, L.P.
To: CREDIT SUISSE AG, CAYMAN ISLANDS BRANCH, AS COLLATERAL AGENT
Reel/Frame 046629/0213 →
ASSIGNMENT OF ASSIGNOR'S INTEREST Recorded Apr 21, 2015
From: BORKAR, SACHIN; GU, QU-MING; MAHONEY, JOSE M; LUO, MINGXIAN; LUSVARDI, KATE MARRITT
To: SOLENIS TECHNOLOGIES, L.P.
Reel/Frame 035457/0944 →