METHOD OF MAKING URETHANE BASED FLUORINATED MONOMERS

• US 20070244289A1
• Filed: 04/13/2006
• Published: 10/18/2007
• Est. Priority Date: 04/13/2006
• Status: Abandoned Application

• Current Assignee: 3M Innovative Properties Company (3M Company)
• Original Assignee: 3M Innovative Properties Company (3M Company)
• Inventors: Kuehneweg, Bernd, Audenaert, Frans
• Application Number:
  US11/279,653
• Publication Number:
  US 20070244289A1
• Time in Patent Office: Days
• US Class Current: 528/44
• CPC Class Codes: C08F 283/006 on to polymers provided for in C08G18/00 C08F283/004 takes precedence
• CPC Class Codes: C08G 18/2885 containing halogen atoms
• CPC Class Codes: C08G 18/5024 containing primary and/or secondary amino groups
• CPC Class Codes: C08G 18/672 Esters of acrylic or alkyl acrylic acid having only one group containing active hydrogen
• CPC Class Codes: C08G 18/673 containing two or more acrylate or alkylacrylate ester groups
• CPC Class Codes: C08G 18/7831 containing biuret groups
• CPC Class Codes: C08G 18/792 formed by oligomerisation of aliphatic and/or cycloaliphatic isocyanates or isothiocyanates
• CPC Class Codes: C09D 175/16 having terminal carbon-to-carbon unsaturated bonds

Abstract

Method of preparing urethane based fluorinated monomers comprising (i) reacting a fluorinated alcohol and an isocyanate functional non-fluorinated monomer or (ii) reacting in one or two steps a fluorinated alcohol, a polyisocyanate and an isocyanate reactive non-fluorinated monomer, wherein reactions (i) and (ii) are carried out in the presence of one or more reactive diluents, the reactive diluents having an ethylenically unsaturated group and being free of isocyanate reactive groups. The method does not require an inert organic solvent as a reaction medium, thus excluding volatile organic compounds (VOC'"'"'s). The resulting compositions can be readily and conveniently used to prepare radiation curable coating compositions without the need to remove organic solvent from the composition.

Claims

1. Method of preparing urethane based fluorinated monomers comprising (i) reacting a fluorinated alcohol and an isocyanate functional non-fluorinated monomer or (ii) reacting in one or two steps a fluorinated alcohol, a polyisocyanate and an isocyanate reactive non-fluorinated monomer, said reactions (i) and (ii) being carried out in the presence of one or more reactive diluents, said reactive diluents having an ethylenically unsaturated group and being free of isocyanate reactive groups.

2. Method according to claim 1 wherein the isocyanate functional non-fluorinated monomer is selected from the group of isocyanate functional non-fluorinated acrylate or methacrylate monomers.

3. Method according to claim 1 wherein said reactions are carried out in absence of a solvent or substantially in absence of a solvent.

4. Method according to claim 1 wherein said fluorinated alcohol is selected from a monofunctional fluorinated alkanol having between 3 and 12 carbon atoms, a perfluoropolyether compound having one or more perfluorinated polyether groups and one or more hydroxyl groups, or an oligomeric fluorinated alcohol of the formula:

M^f_mM^h_n-Q³-(OH)_c

wherein c is 1 or 2, M^f_mM^h_n represents a fluorinated oligomer comprising m units derived from a fluorinated monomer and n units derived from a non-fluorinated monomer m represents a value of 2 to 40, n is 0 to 20, and -Q³-(OH)_c together represents the organic residue obtained by removing a hydrogen atom from a chain transfer agent that is functionalized with one or two hydroxy groups.

5. Method according to claim 1 wherein said reactive diluent is present in an amount of at least 10% based on the total weight of the reactive diluent and reactants.

6. Method according to claim 1 wherein the reactive diluent is liquid at a temperature of about 20°

C.

7. Method according to claim 6 wherein said reactive diluent is selected from monomers having one or more acrylate or methacrylate groups, monomers having one or more vinyl ether groups and N-vinyl amides.

8. Method according to claim 1 wherein isocyanate reactive non-fluorinated monomer comprises a hydroxyl group.

9. Method according to claim 1 wherein said polyisocyanate is selected from one or more aliphatic isocyanates having 2, 3, or 4 isocyanate groups, one or more aromatic isocyanates having 2, 3, or 4 isocyanate groups and mixtures thereof.

10. Method according to claim 1 wherein said two-step reaction of said fluorinated alcohol, a polyisocyanate and an isocyanate reactive non-fluorinated monomer is carried out by reacting in a first step said fluorinated alcohol and said polyisocyanate in a ratio such that a resulting reaction product has one or more isocyanate groups and in a second step reacting the resulting reaction product of the first step with said isocyanate reactive non-fluorinated monomer.