Aqueous thermo-thickening resin solutions

• US 10,538,664 B2
• Filed: 09/10/2015
• Issued: 01/21/2020
• Est. Priority Date: 09/15/2014
• Status: Active Grant

• Current Assignee: BASF Coatings GmbH (BASF SE)
• Original Assignee: BASF Coatings GmbH (BASF SE)
• Inventors: Tazzia, Charles L., Swartzlander, Mark D.
• Primary Examiner(s): McCulley, Megan
• Application Number:
  US15/511,051
• Publication Number:
  US 20170298223A1
• Time in Patent Office: 1,594 Days
• CPC Class Codes: C04B 2103/44 Thickening, gelling or viscosity increasing agents
• CPC Class Codes: C04B 2111/1006 Absence of well-defined organic compounds
• CPC Class Codes: C04B 22/082 Acids
• CPC Class Codes: C04B 24/06 containing hydroxy groups
• CPC Class Codes: C04B 24/281 Polyepoxides
• CPC Class Codes: C04B 24/282 Polyurethanes; Polyisocyanates
• CPC Class Codes: C04B 24/283 Polyesters
• CPC Class Codes: C04B 24/302 Phenol-formaldehyde condensation polymers
• CPC Class Codes: C04B 24/305 Melamine-formaldehyde condensation polymers
• CPC Class Codes: C04B 28/02 containing hydraulic cements other than calcium sulfates
• CPC Class Codes: C08G 2650/50 containing nitrogen, e.g. polyetheramines or Jeffamines(r)
• CPC Class Codes: C08G 2650/56 Polyhydroxyethers, e.g. phenoxy resins
• CPC Class Codes: C08G 59/066 with chain extension or advancing agents
• CPC Class Codes: C08L 63/00 Compositions of epoxy resins; Compositions of derivatives of epoxy resins
• CPC Class Codes: C08L 71/00 Compositions of polyethers obtained by reactions forming an ether link in the main chain of polyacetals C08L59/00; of epoxy resins C08L63/00; of polythioether-ethers C08L81/02; of polyether-sulfones C08L81/06; Compositions of derivatives of such polymers
• CPC Class Codes: C08L 75/12 from compounds containing nitrogen and active hydrogen, the nitrogen atom not being part of an isocyanate group
• CPC Class Codes: C09K 3/00 Materials not provided for elsewhere
• CPC Class Codes: C09K 8/426 for plugging
• CPC Class Codes: C09K 8/512 containing cross-linking agents
• CPC Class Codes: C09K 8/58 Compositions for enhanced recovery methods for obtaining hydrocarbons, i.e. for improving the mobility of the oil, e.g. displacing fluids

Abstract

Provided are aqueous resin solutions having unique rheologies and products incorporating the same. The water-based materials provided herein are thermo-thickening, and the materials increase dramatically in viscosity (at least 100 times) in a desired temperature range increase (20 C to <100 C) at ambient pressure. Suitable resins comprising a hydrophobic group and a hydrophilic group may be selected from an epoxy resin, a phenol-formaldehyde resin, a polyurethane resin, an acrylic resin, a polyester resin, an acrylic-urethane resin, a melamine resin, a melamine-formaldehyde resin, an amino resin, and combinations thereof. A specific epoxy functional resin/polymer suitable for the resin solutions are prepared by reacting (A) an epoxy pre-polymer of (1) one or more polyols and (2) one or more epoxy functional materials with (B) a di- or polyamine, thereby forming the aqueous thermo-thickening resin solution. The resin solutions are substantially free of cross-linking agents.

Claims

1. An aqueous thermo-thickening resin solution for a non-coating application, comprising:

a resin comprising a hydrophobic unit and a hydrophilic unit, wherein a ratio of a number average molecular weight of all of the hydrophobic units to all of the hydrophilic units in the resin is less than 2.5 and wherein the resin is a reaction product consisting of;

(A) an epoxy pre-polymer, consisting of, in reacted form an aromatic polyol, which is bisphenol A (Bis A), an epoxy functional material, which is diglycidyl ether of bisphenol A (DGEBA), and optionally a catalyst, and

(B) a di- or polyamine, which is a polyether amine;

water; and

optionally, a salting component;

the solution being substantially free of a cross-linking agent;

wherein the solution exhibits a reversible dynamic viscosity increase of at least 100 times in a temperature range from 20°

C. to <

100°

C. at ambient pressure.

2. The aqueous thermo-thickening resin solution of claim 1, wherein the salting component is present and is at least one selected from the group consisting of organic acids, mineral acids, and nitrogen-containing compounds.

3. The aqueous thermo-thickening resin solution of claim 1, comprising by weight:

the reaction product in the range of 0.5-60%;

water in the range of 40-99.5%; and

organic volatiles in the range of 0-25%;

wherein the percent neutralization is in the range of 40-110%.

4. A temperature-sensitive product, comprising:

the aqueous thermo-thickening resin solution of claim 1; and

a carrier for the aqueous thermo-thickening resin solution.

5. The temperature-sensitive product of claim 4, wherein the carrier comprises a liquid-impermeable pouch or a plurality of shells of microcapsules;

and wherein a surface of the product becomes more supportive upon contact with a living body.

6. The temperature-sensitive product of claim 4, wherein the carrier comprises another liquid;

and wherein the product thickens during use at temperatures elevated from ambient temperature.

7. The temperature-sensitive product of claim 6, that is an industrial fluid and the resin of the aqueous thermo-thickening resin solution is effective as a rheology control agent.

8. The temperature-sensitive product of claim 4, that is effective to absorb energy, thereby providing protection to an item in its proximity.

9. A method of absorbing energy, the method comprising:

obtaining the temperature-sensitive product of claim 4; and

associating the temperature-sensitive product with an item in the proximity of the temperature-sensitive product such that upon contact with an energy source, the temperature-sensitive product thickens and the item remains substantially intact.

10. A method of providing a temperature-sensitive product for a non-coatings application, the method comprising:

obtaining the aqueous thermo-thickening resin solution of claim 1;

incorporating the aqueous thermo-thickening resin solution with a carrier; and

forming the temperature-sensitive product whose structure changes upon a temperature change to 40−

<

100°

C. at ambient pressure.

11. The aqueous thermo-thickening resin solution of claim 1, wherein the ratio of the number average molecular weight of all of the hydrophobic units to all of the hydrophilic units in the resin is from 0.01 to 0.99.

12. The aqueous thermo-thickening resin solution of claim 1, wherein the ratio of the number average molecular weight of all of the hydrophobic units to all of the hydrophilic units in the resin is from 0.20 to 0.75.

13. A method of making an aqueous thermo-thickening resin solution for a non-coating application, the method comprising:

(I)forming a resin comprising a hydrophobic unit and a hydrophilic unit, wherein a ratio of a number average molecular weight of all of the hydrophobic units to all of the hydrophilic units in the resin is less than 2.5 and wherein the resin is a reaction product consisting of;

(A) an epoxy pre-polymer, consisting of, in reacted form, an aromatic polyol, which is bisphenol A (Bis A), an epoxy functional material, which is diglvcidvl ether of bisphenol A (DGEBA), and optionally a catalyst, and

(B) a di- or polyamine, which is a polyether amine; and

(II) dissolving the resin in water, and optionally, a salting component, in the substantial absence of a cross-linking agent;

thereby forming the aqueous thermo-thickening resin solution that exhibits a reversible kinematic viscosity increase of at least 100 times in a temperature range of 20°

C. to <

100°

C. at ambient temperature.