IP Library Granted Patent US 6,908,983
Granted Patent B2
US 6,908,983 · App. 10/404,940 · Granted Jun 21, 2005

Synthesis of high solids resins from amine terminated polyamides

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Quick Facts
Patent No.
US 6,908,983
App. No.
10/404,940
Granted
Jun 21, 2005
Kind
B2
Abstract

The present invention contemplates a process for forming polyaminoamide polymers formed by the reaction of a dibasic acid/ester with excess amounts of an amine; the intermediate polymer resulting therefrom; a process for synthesizing effective, high solids resins resulting from the reaction of intermediate polymers with an epihalohydrin; and the resultant high, solids resin. These resins may be used as wet strength resins in the papermaking industry.

Claims (41)

1. A process for the synthesis of an intermediate polyamide polymer comprising:

(a) mixing an amount of a dibasic acid or ester and an excess amount of an amine, wherein the diacid/ester:amine mole ratio ranges from about 1:1.125 to about 1:1.175, thereby forming a polymerization mixture; and

(b) allowing the polymerization mixture from step (a) to polymerize to completion.

2. The process according to claim 1 , wherein the dibasic ester comprises at least one of dimethyladipate, dimethylsebacate, dimethylitaconate, dimethylazelate, dimethyloxalate, dimethylglutarate and mixtures thereof.

3. The process according to claim 1 , wherein the dibasic acid comprises at least one of adipic acid, glutaric acid, oxalic acid, succinic acid, azelaic acid, sebacic acid, maleic acid, fumaric acid, itaconic acid and mixtures thereof.

4. The process according to claim 1 , wherein the amine comprises at least one, of diethylene triamine (DETA) or its analogs, N-(3-aminopropyl)-1,3-propanediamine (dipropylene triamine or DPTA), ethylene diamine (EDA), 1,6-hexamethylenediamine (HMDA), triethylene tetraamine (TETA), tetraethylene pentaamine (TEPA), N-methyl-bis(aminopropyl)amine (MBAPA), bis(hexamethylene triamine) (BHMT), tripropylene tetraamine, tetrapropylene pentaamine, spermine, spermidine, 1-phenyl-2,4-pentane diamine, 2-phenyl-1,3-propanediamine, 2-methyl-1,5-pentane diamine, and phenylene diamine and combinations thereof.

5. The process according to claim 4 , wherein the amine comprises at least one of diethylene triamine (DETA), triethylene tetraamine (TETA), tetraethylene pentaamine (TEPA) and combinations thereof.

6. The process according to claim 5 , wherein the amine is diethylene triamine (DETA).

7. The process according to claim 1 , wherein the intermediate polymer has a molecular weight ranging from about 1600 to about 2100 Daltons.

8. The process according to claim 1 , wherein the intermediate polymer is a water-soluble linear condensation polymer.

9. The process according to claim 1 , wherein the intermediate polymer is a water-soluble branched condensation polymer.

10. An intermediate polymer reaction product produced according to the process of claim 1 .

11. An intermediate polymer having a linear formula comprising:

wherein a ranges from 2-8, b ranges from 2-6 and c ranges from 2-6.

12. An intermediate polymer having a branched formula comprising:

wherein a ranges from 2-8, b ranges from 2-6 and c ranges from 2-6.

13. A process for making a high solids polyamide resin comprising:

(a) mixing an amount of a dibasic acid or ester and an excess amount of an amine, wherein the dibasic acid/ester:amine mole ratio ranges from about 1:1.125 to about 1:1.175, thereby forming a polymerization mixture;

(b) allowing the polymerization mixture from step (a) to polymerize to completion;

(c) reacting the polymerization mixture with an epihalohydrin; and

(d) allowing the reaction to proceed wherein the intermediate polymer reaction mixture is cross-linked.

14. The process according to claim 13 , wherein the diester comprises at least one of dimethyladipate, dimethylsebacate, dimethylitaconate, dimethylazelate, dimethyloxalate, dimethylglutarate and mixtures thereof.

15. The process according to claim 13 , wherein the dibasic acid comprises at least one of adipic acid, glutaric acid, oxalic acid, succinic acid, azelaic acid, sebacic acid, maleic acid, fumaric acid, itaconic acid and mixtures thereof.

16. The process according to claim 13 , wherein the amine comprises at least one of diethylene triamine (DETA) or its analogs, N-(3-aminopropyl)-1,3-propanediamine (dipropylene triamine or DPTA), ethylene diamine (EDA), 1,6-hexamethylenediamine (HMDA), triethylene tetraamine (TETA), tetraethylene pentaamine (TEPA), N-methyl-bis(aminopropyl)amine (MBAPA), bis(hexamethylene triamine) (BHMT), tripropylene tetraamine, tetrapropylene pentaamine, spermine, spermidine, 1-phenyl-2,4-pentane diamine, 2-phenyl-1,3-propanediamine, 2-methyl-1,5-pentane diamine, and phenylene diamine and combinations thereof.

17. The process according to claim 16 , wherein the amine comprises at least one of diethylene triamine (DETA), triethylene tetraamine (TETA), tetraethylene pentaamine (TEPA) and combinations thereof.

18. The process according to claim 17 , wherein the amine is diethylene triamine (DETA).

19. The process according to claim 13 , wherein the epihalohydrin is epichlorohydrin.

20. The process according to claim 13 , wherein the high solids resin has a solids content in the range of about 30-50 wt.-%.

21. The process according to claim 20 , wherein the high solids resin has a solids content in the range of about 30-45 wt.-%.

22. The process according to claim 21 , wherein the high solids resin has a solids content in the range of about 3941 wt.-%.

23. The process according to claim 13 , wherein the intermediate polymer of step b) is cross-linked with itself.

24. The process according to claim 13 , wherein the intermediate polymer of step b) is cross-linked with another material.

25. A high solids polyamide resin produced according to the process of claim 13 .

26. A high solids polyamide resin having a linear formula comprising:

wherein a ranges from 2-8, b ranges from 2-6 and c ranges from 2-6.

27. A high solids polyamide resin having a branched formula comprising:

wherein a ranges from 2-8, b ranges from 2-6 and c ranges from 2-6.

28. A wet strength agent produced by the process of claim 13 .

29. A creping aid produced by the process of claim 13 .

30. A cellulosic product comprising the resin of claim 26 .

31. A cellulosic product comprising the resin of claim 27 .

Assignments (28)
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 →
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 →
SECURITY AGREEMENT (ABL) Recorded Sep 14, 2022
From: SOLENIS TECHNOLOGIES, L.P.; INNOVATIVE WATER CARE, LLC
To: BANK OF AMERICA, N.A, AS COLLATERAL AGENT
Reel/Frame 061432/0958 →
SECURITY AGREEMENT (TERM) Recorded Sep 13, 2022
From: SOLENIS TECHNOLOGIES, L.P.; INNOVATIVE WATER CARE, LLC
To: GOLDMAN SACHS BANK USA, AS COLLATERAL AGENT
Reel/Frame 061431/0851 →
SECURITY AGREEMENT (NOTES) Recorded Sep 13, 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 061431/0865 →
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: CREDIT SUISSE AG, CAYMAN ISLANDS BRANCH
To: SOLENIS TECHNOLOGIES, L.P.
Reel/Frame 058856/0724 →
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: CITIBANK, N.A.
To: SOLENIS TECHNOLOGIES, L.P.
Reel/Frame 058848/0636 →
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 →
INTELLECTUAL PROPERTY SECOND LIEN SECURITY AGREEMENT RELEASE Recorded Jul 20, 2018
From: BANK OF AMERICA, N.A., AS COLLATERAL AGENT
To: SOLENIS TECHNOLOGIES, L.P.
Reel/Frame 047058/0800 →
INTELLECTUAL PROPERTY FIRST LIEN SECURITY AGREEMENT RELEASE Recorded Jul 20, 2018
From: CREDIT SUISSE AG, CAYMAN ISLANDS BRANCH, AS COLLATERAL AGENT
To: SOLENIS TECHNOLOGIES, L.P.
Reel/Frame 046594/0252 →
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 →
NOTICE AND CONFIRMATION OF GRANT OF SECURITY INTEREST IN PATENTS (SECOND LIEN) Recorded Aug 14, 2014
From: SOLENIS TECHNOLOGIES, L.P.
To: BANK OF AMERICA, N.A., AS COLLATERAL AGENT
Reel/Frame 033535/0847 →
NOTICE AND CONFIRMATION OF GRANT OF SECURITY INTEREST IN PATENTS (FIRST LIEN) Recorded Aug 14, 2014
From: SOLENIS TECHNOLOGIES, L.P.
To: CREDIT SUISSE AG, CAYMAN ISLANDS BRANCH, AS COLLATERAL AGENT
Reel/Frame 033535/0806 →
U.S. ASSIGNMENT OF PATENTS Recorded Aug 4, 2014
From: HERCULES INCORPORATED
To: SOLENIS TECHNOLOGIES, L.P.
Reel/Frame 033470/0922 →
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 →
SECURITY AGREEMENT Recorded Sep 16, 2011
From: ASHLAND LICENSING AND INTELLECTUAL PROPERTY LLC; HERCULES INCORPORATED; AQUALON COMPANY; ISP INVESTMENT INC.
To: THE BANK OF NOVA SCOTIA, AS ADMINISTRATIVE AGENT
Reel/Frame 026918/0052 →
RELEASE OF PATENT SECURITY AGREEMENT Recorded Sep 15, 2011
From: BANK OF AMERICA, N.A.
To: ASHLAND, INC.; ASHLAND LICENSING AND INTELLECTUAL PROPERTY LLC; AQUALON COMPANY; HERCULES INCORPORATED
Reel/Frame 026927/0247 →
SECURITY AGREEMENT Recorded Apr 14, 2010
From: ASHLAND LICENSING AND INTELLECTUAL PROPERTY LLC; AQUALON COMPANY; HERCULES INCORPORATED
To: BANK OF AMERICA, N.A., AS ADMINISTRATIVE AGENT
Reel/Frame 024225/0289 →
RELEASE OF SECURITY INTEREST Recorded Apr 13, 2010
From: BANK OF AMERICA, N.A., AS COLLATERAL AGENT
To: ASHLAND LICENSING AND INTELLECTUAL PROPERTY LLC; AQUALON COMPANY; HERCULES INCORPORATED
Reel/Frame 024218/0928 →
SECURITY AGREEMENT Recorded Dec 3, 2008
From: ASHLAND LICENSING AND INTELLECTUAL PROPERTY...; AQUALON COMPANY; HERCULES INCORPORATED
To: BANK OF AMERICA, N.A. AS ADMINISTRATIVE AGENT
Reel/Frame 021924/0001 →
PATENT TERMINATION CS-014683-0542 Recorded Dec 1, 2008
From: CREDIT SUISSE, CAYMAN ISLANDS BRANCH
To: HERCULES INCORPORATED
Reel/Frame 021901/0464 →
NOTICE OF GRANT OF SECURITY INTEREST Recorded Jun 3, 2004
From: HERCULES INCORPORATED
To: CREDIT SUISSE FIRST BOSTON, AS COLLATERAL AGENT
Reel/Frame 014683/0542 →
ASSIGNMENT OF ASSIGNOR'S INTEREST Recorded Jul 25, 2003
From: MASLANKA, WILLIAM W.
To: HERCULES INCORPORATED
Reel/Frame 014323/0289 →