Stabilized monomer adhesive compositions

Abstract

A method of sterilizing a polymerizable monomeric adhesive composition includes: providing a polymerizable monomeric adhesive composition in a container, the polymerizable monomeric adhesive composition including a polymerizable 1,1-disubstituted ethylene monomer and at least one stabilizer; holding the composition in the container for a pre-determined amount of time, which is sufficient to inhibit or eliminate polymerization of the monomer during or immediately after sterilization, before sterilizing the composition; and sterilizing the polymerizable monomeric adhesive composition inside the container.

What is claimed is:  
     
         1 . A polymerizable monomeric adhesive composition comprising a polymerizable 1,1-disubstituted ethylene monomer in a liquid phase and in a vapor phase, at least one vapor phase anionic stabilizer, and at least one liquid phase anionic stabilizer, 
 wherein said at least one liquid phase anionic stabilizer is a strong acid and    wherein said at least one vapor phase anionic stabilizer is at least one member selected from the group consisting of boron trifluoride and hydrogen fluoride.    
     
     
         2 . The composition of  claim 1 , wherein said monomer is at least one member selected from the group consisting of n-butyl cyanoacrylate, 2-octyl cyanoacrylate, ethyl cyanoacrylate, methyl cyanoacrylate, ethoxyethyl cyanoacrylate, and methoxyethyl cyanoacrylate.  
     
     
         3 . The composition of  claim 1 , wherein said at least one vapor phase anionic stabilizer comprises boron trifluoride.  
     
     
         4 . The composition of  claim 1 , wherein said at least one liquid phase anionic stabilizer comprises an organic sulfonic acid.  
     
     
         5 . The composition of  claim 4 , wherein said sulfonic acid is present in said composition in a concentration of 1-200 parts per million.  
     
     
         6 . The composition of  claim 1 , wherein said at least one vapor phase anionic stabilizer comprises boron trifluoride and said at least one liquid phase anionic stabilizer comprises a sulfonic acid.  
     
     
         7 . A container containing the composition of  claim 1 .  
     
     
         8 . The container of  claim 7 , wherein said container is made from at least one material selected from the group consisting of glass, plastic, and metal.  
     
     
         9 . The container of  claim 8 , wherein said container is made from plastic.  
     
     
         10 . The composition of  claim 1 , further comprising a secondary anionic active agent.  
     
     
         11 . The composition of  claim 10 , wherein the secondary anionic active agent is selected from the group consisting of phosphoric acid, acetic acid, benzoic acid, chloroacetic acid, and cyanoacetic acid.  
     
     
         12 . The composition of  claim 1 , further comprising at least one medicament.  
     
     
         13 . A method of making a sterile polymerizable α-cyanoacrylate monomer adhesive composition, comprising: 
 dispensing the composition of  claim 1  into a container,  
 sealing said container, and  
 sterilizing the composition and the container.  
 
     
     
         14 . The method of  claim 13 , wherein said sterilizing is by dry heat, gamma irradiation, electron beam irradiation, or microwave irradiation.  
     
     
         15 . The method of  claim 14 , wherein said sterilizing is by dry heat.  
     
     
         16 . The method of  claim 14 , wherein said sterilizing is by gamma irradiation.  
     
     
         17 . The method of  claim 13 , wherein the sterilized composition has a viscosity less than 300% of the viscosity before sterilizing.  
     
     
         18 . The method of  claim 17 , wherein the sterilized composition has a viscosity less than 150% of the viscosity before sterilizing.  
     
     
         19 . The method of  claim 13 , wherein said composition has a total volume of less than 1 milliliter.  
     
     
         20 . The method of  claim 13 , wherein said composition has a total volume of about 0.6 milliliter.  
     
     
         21 . A sterile adhesive composition made by the method of  claim 13 .  
     
     
         22 . A sterile adhesive composition made by the method of  claim 18 .  
     
     
         23 . A polymerized composition made from the composition of  claim 1 .  
     
     
         24 . A polymerized composition made from the composition of  claim 10 .  
     
     
         25 . A polymerized composition made from the composition of  claim 12 .  
     
     
         26 . The method of  claim 13 , wherein the composition further comprises a secondary anionic active agent.  
     
     
         27 . The method of  claim 26 , wherein the secondary anionic active agent is selected from the group consisting of phosphoric acid, acetic acid, benzoic acid, chloroacetic acid, and cyanoacetic acid.  
     
     
         28 . A sterile composition made by the method of  claim 27 .  
     
     
         29 . A polymerizable monomeric adhesive composition comprising a polymerizable 1,1-disubstituted ethylene monomer in a liquid phase and in a vapor phase, at least one vapor phase anionic stabilizer, at least one liquid phase anionic stabilizer, and at least one free radical stabilizer, 
 wherein said at least one liquid phase anionic stabilizer is a strong acid and    wherein said at least one vapor phase anionic stabilizer is at least one member selected from the group consisting of boron trifluoride and hydrogen fluoride.    
     
     
         30 . The adhesive composition of  claim 29 , wherein said at least one free radical stabilizer is selected from the group consisting of butylated hydroxyanisole and butylated hydroxytoluene.  
     
     
         31 . A method of making an adhesive composition comprising: 
 combining a pre-formed polymerizable monomer with at least one vapor phase anionic stabilizer, at least one liquid phase anionic stabilizer, and at least one free radical stabilizer to form said adhesive composition.    
     
     
         32 . A method of making a sterile polymerizable 1,1-disubstituted monomer adhesive composition comprising at least one medicament, comprising: 
 dispensing the composition of  claim 12  into a container,    sealing said container, and    sterilizing the composition and the container.    
     
     
         33 . The composition made by the method of  claim 32 .  
     
     
         34 . A kit comprising the composition of  claim 33 .  
     
     
         35 . A method of treating a wound comprising: 
 applying the composition of  claim 1  to a wound, and    allowing the composition to polymerize.    
     
     
         36 . A method of treating a wound comprising: 
 applying the composition of  claim 10  to a wound, and    allowing the composition to polymerize.    
     
     
         37 . A method of treating a wound, comprising: 
 applying the composition of  claim 13  to a wound, and    allowing the composition to polymerize.    
     
     
         38 . A method of treating a wound, comprising: 
 applying at least one medicament to a wound surface, and    applying the composition of  claim 1  over said at least one medicament to form an adhesive composition, thus treating the wound.    
     
     
         39 . A method of making a polymerizable monomeric adhesive composition, comprising: 
 dispensing the composition of  claim 1  into a container, and    sealing said container.    
     
     
         40 . The composition of  claim 1 , wherein said strong acid has an aqueous pK a  less than 2.  
     
     
         41 . The composition of  claim 40 , wherein said strong acid is selected from the group consisting of strong mineral acids and strong organic acids.  
     
     
         42 . The composition of  claim 40 , wherein said strong acid is a strong mineral acid.  
     
     
         43 . The composition of  claim 40 , wherein said strong acid is a strong organic acid.  
     
     
         44 . The adhesive composition of  claim 29 , wherein said strong acid has an aqueous pK a  less than 2.  
     
     
         45 . The adhesive composition of  claim 44 , wherein said strong acid is selected from the group consisting of strong mineral acids and strong organic acids.  
     
     
         46 . The adhesive composition of  claim 44 , wherein said strong acid is a strong mineral acid.  
     
     
         47 . The adhesive composition of  claim 44 , wherein said strong acid is a strong organic acid.  
     
     
         48 . The method of  claim 42 , wherein said at least one liquid phase anionic stabilizer is a strong acid having an aqueous pK a  less than 2.  
     
     
         49 . The method of  claim 48 , wherein said strong acid is selected from the group consisting of strong mineral acids and strong organic acids.  
     
     
         50 . The method of  claim 48 , wherein said strong acid is a strong mineral acid.  
     
     
         51 . The method of  claim 48 , wherein said strong acid is a strong organic acid.