Aqueous-based polyurethane compositions and method of preparation

• US 4,442,259 A
• Filed: 04/26/1982
• Issued: 04/10/1984
• Est. Priority Date: 04/26/1982
• Status: Expired due to Term

• Current Assignee: Hampshire Chemical Corp. (Dow, Inc.)
• Original Assignee: WR Grace & Company
• Inventors: Isgur, Irving E., DelVecchio, William D.
• Primary Examiner(s): Schofer, Joseph L.
• Assistant Examiner(s): Sarofim, N.
• Application Number:
  US06/371,631
• Time in Patent Office: 715 Days
• Field of Search: 524/839, 524/591
• US Class Current: 524/839
• CPC Class Codes: B32B 2037/1276 water-based adhesive
• CPC Class Codes: B32B 7/12 using interposed adhesives or interposed materials with bonding properties
• CPC Class Codes: C08G 18/10 Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step
• CPC Class Codes: C08G 18/2805 Compounds having only one group containing active hydrogen vinylpolymers having terminal groups containing active hydrogen C08G18/62
• CPC Class Codes: C08G 18/302 Water
• CPC Class Codes: C08G 18/4833 Polyethers containing oxyethylene units
• CPC Class Codes: C09J 175/08 from polyethers

Abstract

Aqueous-based polyurethane elastomer compositions which can be used as adhesives and a method of preparing same are described. The polyurethane compositions are prepared by chain extending an isocyanate-terminated urethane prepolymer with an equivalent excess of water in the presence of a monofunctional isocyanate group blocking agent to provide a reaction mixture having a desired adhesive capability and thereafter adding additional blocking agent to the reaction mixture in an equivalent amount at least substantially equal to the remaining equivalent amount of unreacted isocyanate groups in the prepolymer.

Claims

1. A method of preparing an aqueous based polyurethane adhesive solution comprising the steps of:

providing a reaction mixture comprising an isocyanate-terminated urethane prepolymer and an equivalent excess of water, based on the isocyanate content of said prepolymer;

reacting said prepolymer and said water to effect chain extension of said prepolymer;

controlling the rate of said chain extension by adding to said reaction mixture a monofunctional isocyanate group blocking agent and permitting reaction between said agent and isocyanate groups in said prepolymer;

permitting said prepolymer and said water to react until said reaction mixture acquires a desired adhesive capability; and

adding to said reaction mixture additional said monofunctional isocyanate group blocking agent or a second isocyanate group blocking agent in an amount at least substantially equal to the remaining unreacted isocyanate groups in said prepolymer on an equivalent basis.

2. A method of claim 1 wherein said equivalent excess of water is at least a two-fold excess.

3. A method of claim 1 wherein said prepolymer comprises the reaction product of a hydrophilic polyol and a polyisocyanate.

4. A method of claim 3 wherein said polyol is a polyoxyethylene polyol.

5. A method of claim 4 wherein said polyoxyethylene polyol is polyethylene glycol.

6. A method of claim 3 wherein said polyisocyanate is a diisocyanate.

7. A method of claim 1 wherein said monofunctional blocking agent is selected from the group consisting of alcohols, primary amines, secondary amines, oximes, and alkanol amines.

8. A method of claim 1 wherein said monofunctional blocking agent is less reactive with said prepolymer than water and an equivalent excess, based on the isocyanate content of said prepolymer, is used to control the rate of said chain extension.

9. A method of claim 8 wherein said monofunctional blocking agent is an alcohol.

10. A method of claim 9 wherein said alcohol is ethanol.

11. A method of claim 1 wherein said monofunctional blocking agent is more reactive with said prepolymer than water and less than an equivalent amount, based on the isocyanate content of said prepolymer, is added to control the rate of said chain extension.

12. A method of claim 11 wherein said blocking agent is an oxime.

13. A method of claim 1 wherein said additional monofunctional blocking agent or said second blocking agent is added in an equivalent excess based on the equivalents of said remaining unreacted isocyanate groups.

14. A method of claim 1 wherein said second isocyanate group blocking agent is selected from the group consisting of monofunctional and polyfunctional alcohols, primary amines, secondary amines, and oximes;

alkanol amines; and

ammonia.

15. A method of claim 14 wherein said second blocking agent comprises, in combination, a monofunctional alcohol and ammonia.

16. An aqueous based, cold seal, polyurethane adhesive solution prepared by a method comprising the steps of:

providing a reaction mixture comprising an isocyanate-terminated urethane prepolymer and an equivalent excess of water, based on the isocyanate content of said prepolymer;

reacting said prepolymer and said water to effect chain extension of said prepolymer;

controlling the rate of said chain extension by adding to said reaction mixture a monofunctional isocyanate group blocking agent and permitting reaction between said agent and isocyanate groups in said prepolymer;

permitting said prepolymer and said water to react until said reaction mixture acquires a desired adhesive capability; and

adding to said reaction mixture additional said monofunctional isocyanate group blocking agent or a second isocyanate group blocking agent in an amount at least substantially equal to the remaining unreacted isocyanate groups in said prepolymer on an equivalent basis.

17. A composition of claim 16 wherein said equivalent excess of water is at least a two-fold excess.

18. A composition of claim 16 wherein said prepolymer comprises the reaction product of a hydrophilic polyoxyethylene polyol and a polyisocyanate.

19. A composition of claim 16 wherein said monofunctional blocking agent is selected from the group consisting of alcohols, primary amines, secondary amines, oximes, and alkanol amines.

20. A composition of claim 19 wherein said monofunctional blocking agent is an alcohol which is added in an equivalent excess, based on the isocyanate content of said prepolymer, to control the rate of said chain extension.

21. A composition of claim 16 wherein said additional monofunctional blocking agent or said second blocking agent is added in an equivalent excess, based on the equivalents of said remaining unreacted isocyanate groups.

22. A composition of claim 16 comprising, as a water-miscible cosolvent added prior to, during, or subsequent to reaction of said water and said prepolymer, methanol, ethanol, isopropanol, acetone, or methyl ethyl ketone.

23. A composition of claim 16 comprising a carrier solvent comprising at least 10% by weight of water.

24. A method of cold seal bonding a first substrate to a second substrate comprising the steps of:

coating a surface of said first substrate with an aqueous based, cold seal polyurethane adhesive composition prepared by a method comprising the steps of reacting an isocyanate-terminated urethane prepolymer with an equivalent excess of water, based on the isocyanate content of said prepolymer, in the presence of a monofunctional isocyanate group blocking agent;

permitting said prepolymer and said water to react until the reaction mixture acquires a desired adhesive capability; and

adding to said reaction mixture additional said monofunctional isocyanate group blocking agent or a second isocyanate group blocking agent in an amount at least substantially equal to the remaining unreacted isocyanate groups in said prepolymer on an equivalent basis;

drying the adhesive coating; and

contacting said second substrate with said coating.

25. A method of claim 24 further comprising coating said adhesive composition on a surface of said second substrate, drying the adhesive coating on said second substrate, and contacting the respective adhesive coatings on said first and second substrates.

26. A method of claim 24 wherein said first and second substrates are selected from the group consisting of paper, metal, polyurethane foam, synthetic polymer sheets, and synthetic polymer fibers.