Adhesive beads

• US 9,657,205 B2
• Filed: 02/03/2014
• Issued: 05/23/2017
• Est. Priority Date: 02/01/2013
• Status: Active Grant

• Current Assignee: Carolyn Dry
• Original Assignee: Carolyn Dry
• Inventors: Dry, Carolyn
• Primary Examiner(s): SASTRI, SATYA B
• Application Number:
  US14/764,503
• Publication Number:
  US 20150361314A1
• Time in Patent Office: 1,205 Days
• Field of Search: None
• CPC Class Codes: B01J 13/06 by phase separation
• CPC Class Codes: B01J 13/18 In situ polymerisation with all reactants being present in the same phase
• CPC Class Codes: C08K 5/09 Carboxylic acids; Metal salts thereof; Anhydrides thereof
• CPC Class Codes: C08K 5/095 Carboxylic acids containing halogens
• CPC Class Codes: C08K 5/13 Phenols; Phenolates
• CPC Class Codes: C08K 9/10 Encapsulated ingredients
• CPC Class Codes: C09B 67/0013 with polymeric coatings
• CPC Class Codes: C09B 67/0097 Dye preparations of special physical nature; Tablets, films, extrusion, microcapsules, sheets, pads, bags with dyes
• CPC Class Codes: C09D 7/65 macromolecular C09D7/41-C09D7/48 take precedence
• CPC Class Codes: C09D 7/70 characterised by shape, e.g. fibres, flakes or microspheres
• CPC Class Codes: C09J 11/02 Non-macromolecular additives
• CPC Class Codes: C09J 11/06 organic
• CPC Class Codes: C09J 11/08 Macromolecular additives
• CPC Class Codes: C09J 151/003 grafted on to macromolecular compounds obtained by reactions only involving unsaturated carbon-to-carbon bonds C09J151/04, C09J151/06 take precedence
• CPC Class Codes: C09J 2301/412 presence of microspheres
• CPC Class Codes: C09J 4/00 Adhesives based on organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond ; adhesives, based on monomers of macromolecular compounds of groups C09J183/00 - C09J183/16
• CPC Class Codes: C09J 9/00 Adhesives characterised by their physical nature or the effects produced, e.g. glue sticks C09J7/00 takes precedence
• CPC Class Codes: Y10T 428/2998 including synthetic resin or polymer

Abstract

The present technology provides for adhesive beads, comprising a shell and a core wherein the core comprises one or more cyanoacrylate monomers and the shell comprises a polycyanoacrylate of the same one or more cyanoacrylate monomers. The present technology further provides for methods of making and using the adhesive beads.

Claims

1. A bead comprising a shell and core wherein

the core comprises one or more cyanoacrylate monomers and an acid, wherein the acid comprises a mineral acid, a sulfonimide, an alkyl carboxylic acid, an aryl carboxylic acid, a perfluorocarboxylic acid, a halogenated phenol, a perfluoroalcohol, RSO₃H, or (R′

SO₂)₂NH;

where R and R′

are independently selected from the group consisting of alkyl, alkenyl, aryl, heteroaryl, perfluoroalkyl, and perfluoroarylakyl, and

the shell comprises a polycyanoacrylate of the same one more cyanoacrylate monomers, wherein the one or more cyanoacrylate monomers are selected from methyl cyanoacrylate, ethyl cyanoacrylate, butyl cyanoacrylate, octyl cyanoacrylate, beta-methoxyethyl cyanoacrylate, or a mixture of any two or more thereof.

2. The bead of claim 1, wherein the core is liquid and the shell is solid.

3. The bead of claim 1, wherein the one or more cyanoacrylate monomers have a viscosity of 1 centipoise to 1000 centipoise.

4. The bead of claim 1, wherein the one or more cyanoacrylate monomers have set times from 1 second to 3 minutes.

5. The bead of claim 1, wherein the core further comprises one or more of glycidyl acrylate, epichlorohydrin, 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexane carboxylate, silicon-containing monomers, fluoro-containing monomers, ionizable monomers, and poly(methyl methacrylate).

6. The bead of claim 1, comprising one or more additives selected from a filler, stabilizer, viscosity modifier, colorant, rubberizer, odorant, plasticizer, or any combination of two or more thereof.

7. The bead of claim 6, wherein the filler comprises polymer, metal, glass or carbon fibers or particles, magnetic particles, carbon nanotubes, carbon black, silicas, nanoparticles, nanoflakes, or any combination of two or more thereof.

8. The bead of claim 1, wherein the acid comprises HCl, HF, HBr, H₂SO₄, H₃PO₄, HNO₃, perchloric acid, acetic acid, chloroacetic acid, cyanoacetic acid, formic acid, benzoic acid, bis(trifluoromethane)sulfonimide, chlorophenol, trifluroacetic acid, pentafluoropropionic acid, ethanesulfonic acid, toluenesulfonic acid, methane sulfonic acid, trifluoromethanesulfonic acid, fluorosulfonic acid, chlorosulfonic acid, nitrobenzenesulfonic acid, dinitrobenzenesulfonic acid, bromobenzenesulfonic acid, chlorobenzenesulfonic acid, benzenesulfonic acid, ethylbenzenesulfonic acid, 2-mesitylenesulfonic acid, p-xylene-2-sulfonic acid, naphthalenesulfonic acid or any combination of two or more thereof.

9. The bead of claim 1, wherein the bead has a diameter ranging from 100 μ

m to 3000 μ

m.

10. The bead of claim 1, wherein the shell has a thickness in a range from 1 μ

m to 150 μ

m.

11. A composition comprising the bead of claim 1 and a liquid, a paint, or a coating.

12. An article comprising the bead of claim 1, wherein the article is selected from a fastener, a medical device, a construction material or a construction plenum.

13. A composite comprising a matrix polymer and a plurality of the beads of claim 1.

14. The composite of claim 13 wherein the matrix polymer is selected from the group consisting of thermosetting resins, thermoplastics, and elastomers.

15. A method of preparing a bead of claim 1 comprising:

adding a base to a heterogeneous mixture comprising the one or more cyanoacrylate monomers, the acid, and a fluid in which the one or more cyanoacrylate monomers are substantially insoluble, and

forming a bead comprising the shell surrounding the core.

16. The method of claim 15, wherein the fluid is water or an organic solvent selected from pentane, hexanes, xylene, toluene, ethyl ether, methyl t-butyl ether or a combination of any two or more thereof.

17. The method of claim 15, wherein the base is an aqueous solution comprising hydroxide, amine, acetate, formate, benzoate, bisulfate, fluoride, monobasic phosphate, dibasic phosphate, pyridine, ammonia, or methylamine.

18. The method of claim 15, comprising quenching the bead formation by adding enough acid to lower the pH to 7 or below.

19. The method of claim 15, comprising cooling the heterogeneous mixture to a temperature from 5°

to 15°

C.

20. The method of claim 15, wherein the heterogeneous mixture comprises filler and/or one or more additives.

21. The method of claim 15, wherein the heterogeneous mixture comprises surfactant.

22. The method of claim 15, wherein the one or more cyanoacrylate monomers have set times from 1 second to 3 minutes.

23. A method of preparing the bead of claim 1 comprising:

forming droplets of the one or more cyanoacrylate monomers and/or oligomer in air, the droplets comprising the acid, and

coating the droplets with an alkaline aqueous solution to form the bead.

24. The method of claim 15, wherein the viscosity of the one or more cyanoacrylate monomers is from 1 centipoise to 1000 centipoise.

25. The method of claim 15 comprising forming the heterogenous mixture by adding the one or more cyanoacrylate monomers and/or oligomers to water, below the surface of the water.

26. The method of claim 15, wherein the core of the bead is liquid and the shell of the bead is solid.

27. The method of claim 15, wherein the acid comprises HCl, HF, HBr, H₂SO₄, H₃PO₄, HNO₃, perchloric acid, acetic acid, chloroacetic acid, cyanoacetic acid, formic acid, benzoic acid, bis(trifluoromethane)sulfonimide, chlorophenol, trifluroacetic acid, pentafluoropropionic acid, ethanesulfonic acid, toluenesulfonic acid, methane sulfonic acid, trifluoromethanesulfonic acid, fluorosulfonic acid, chlorosulfonic acid, nitrobenzenesulfonic acid, dinitrobenzenesulfonic acid, bromobenzenesulfonic acid, chlorobenzenesulfonic acid, benzenesulfonic acid, ethylbenzenesulfonic acid, 2-mesitylenesulfonic acid, p-xylene-2-sulfonic acid, naphthalenesulfonic acid or any combination of two or more thereof.

28. The method of claim 23, wherein the core of the bead is liquid and the shell of the bead is solid.

29. The method of claim 23, wherein the acid comprises HCl, HF, HBr, H₂SO₄, H₃PO₄, HNO₃, perchloric acid, acetic acid, chloroacetic acid, cyanoacetic acid, formic acid, benzoic acid, bis(trifluoromethane)sulfonimide, chlorophenol, trifluroacetic acid, pentafluoropropionic acid, ethanesulfonic acid, toluenesulfonic acid, methane sulfonic acid, trifluoromethanesulfonic acid, fluorosulfonic acid, chlorosulfonic acid, nitrobenzenesulfonic acid, dinitrobenzenesulfonic acid, bromobenzenesulfonic acid, chlorobenzenesulfonic acid, benzenesulfonic acid, ethylbenzenesulfonic acid, 2-mesitylenesulfonic acid, p-xylene-2-sulfonic acid, naphthalenesulfonic acid or any combination of two or more thereof.

30. The method of claim 23, wherein the one or more cyanoacrylate monomers have set times from 1 second to 3 minutes.

31. The method of claim 23, wherein the viscosity of the one or more cyanoacrylate monomers is from 1 centipoise to 1000 centipoise.

32. The bead of claim 1, wherein

the acid comprises HCl, HBr, H₂SO₄, H₃PO₄, or any combination of two or more thereof;

and

the one or more cyanoacrylate monomers includes at least ethyl 2-cyanoacrylate.

33. A bead comprising a shell and core wherein

the core comprises one or more cyanoacrylate monomers and an acid, wherein the acid comprises a mineral acid, a sulfonimide, an alkyl carboxylic acid, an aryl carboxylic acid, a perfluorocarboxylic acid, a halogenated phenol, a perfluoroalcohol, RSO₃H, or (R'"'"'SO₂)₂NH;

where R and R′

are independently selected from the group consisting of alkyl, alkenyl, aryl, heteroaryl, perfluoroalkyl, and perfluoroarylakyl, and

the shell comprises a polycyanoacrylate of the same one more cyanoacrylate monomers,

wherein the one or more cyanoacrylate monomers is selected from one or more of methyl 2-cyanoacrylate, ethyl 2-cyanoacrylate, n-butyl 2-cyanoacrylate, 2-octyl 2-cyanoacrylate, 6-methylheptyl 2-cyanoacrylate, fluoroalkyl-2-cyanoacrylate, aryloxy ethyl-2-cyanoacrylate, trimethylsilyl alkyl-2-cyanoacrylate or a mixture of any two or more thereof.

35. The bead of claim 33, wherein the one or more cyanoacrylate monomers is selected from one or more of methyl 2-cyanoacrylate, ethyl 2-cyanoacrylate, n-butyl 2-cyanoacrylate, 2-octyl 2-cyanoacrylate, 6-methylheptyl 2-cyanoacrylate, fluoroalkyl-2-cyanoacrylate, aryloxy ethyl-2-cyanoacrylate, trimethylsilyl alkyl-2-cyanoacrylate or a mixture of any two or more thereof.

34. A bead comprising a shell and core wherein

the core comprises one or more cyanoacrylate monomers and an acid, wherein the acid comprises a mineral acid, a sulfonimide, an alkyl carboxylic acid, an aryl carboxylic acid, a perfluorocarboxylic acid, a halogenated phenol, a perfluoroalcohol, RSO₃H, or (R'"'"'SO₂)₂NH;

where R and R′

are independently selected from the group consisting of alkyl, alkenyl, aryl, heteroaryl, perfluoroalkyl, and perfluoroarylakyl, and

the shell comprises a polycyanoacrylate of the same one more cyanoacrylate monomers,

a second shell enclosing the shell, wherein the second shell comprises a polymer other than cyanoacrylate.