Ethylenically unsaturated, florine-containing urethane derivatives and process for their preparation

• US 5,210,274 A
• Filed: 02/25/1991
• Issued: 05/11/1993
• Est. Priority Date: 02/27/1990
• Status: Expired due to Fees

• Current Assignee: Hoechst Aktiengesellschaft (Sanofi )
• Original Assignee: Hoechst Aktiengesellschaft (Sanofi )
• Inventors: Huth, Hans-Ullrich
• Primary Examiner(s): Schofer, Joseph L.
• Assistant Examiner(s): NAGUMO, MARK
• Application Number:
  US07/661,052
• Time in Patent Office: 806 Days
• Field of Search: 560/167, 560/163, 560/162, 560/160, 560/158, 560/159, 560/167, 560/115, 560/24, 560/25, 560/26
• US Class Current: 560/26
• CPC Class Codes: C07C 271/12 to hydrogen atoms or to carbon atoms of unsubstituted hydrocarbon radicals
• CPC Class Codes: C07C 271/16 to carbon atoms of hydrocarbon radicals substituted by singly-bound oxygen atoms
• CPC Class Codes: C07C 271/28 to a carbon atom of a non-condensed six-membered aromatic ring

Abstract

Ethylenically unsaturated, fluorine-containing urethane derivatives (see Formula I) whose urethane group is substituted on its carboxyl radical by a fluorinated organic radical and on its nitrogen atom by an unfluorinated, ethylenically unsaturated organic radical. Their preparation can be carried out by reacting ethylenically unsaturated, unfluorinated isocyanates with fluorinated organic hydroxyl compounds in bulk in the absence of water or advantageously in inert organic solvents or in ethylenically unsaturated monomers capable of polymerization which behave inertly under the reaction conditions, it being possible to obtain the urethane derivatives directly in liquid or highly viscous or waxy or solid or crystalline form.

Urethane derivatives prepared according to the invention are usually readily to very readily soluble in standard nonaqueous, nonpolar inert organic solvents or in various monomers capable of copolymerization. They can be polymerized or copolymerized in a free-radical way and used to prepare polymers or copolymers.

Claims

1. An ethylenically unsaturated, fluorine-containing urethane derivative of the Formula I, ##STR9## in which R¹ to R⁴, A and the numerical index x have the following meanings:

R¹, R² and R³, which may be identical or different, are H, --CH₃,

x is 1 or 2

A is --(CH₂)_y --, y is 1 to 6, tert-butylphenylene--[C₆ H₃ --C(CH₃)₃ ]-- or --C₆ H₄ C(CH₃)₂ -- or ##STR10## where Z is oxygen or NH,

R⁵ is H, --CH₃, --C₂ H₅,

B is (C₆ -C₁₆)arylene which may contain (C₁ -C₁₀)alkyl radicals, (C₂ -C₁₂)alkylen or (C₆ -C₁₀)cycloalkylene,

k, m, p are 0 or 1,

n is 1 to 5,

R⁴ is --(C₂ F₄)_q H, --(CF₂)_r H, --C_r F_2r --O--R⁶,

q is 1 to 6,

r is 1 to 9,

R⁵ is (C₁ -C₁₂)alkyl which may be partially or fully substituted by fluorine atoms, or is (C₆ -C₁₂)aryl or (C₇ -C₁₂)alkaryl which may be partially or fully substituted by

2. A urethane derivative as claimed in claim 1, wherein, in Formula I, R¹ and R² are H, R³ is H or --CH₃, or R¹ and R³ are H, R² is --CH₃ and Z is oxygen.

3. A process for the preparation of ethylenically unsaturated, fluorine-containing urethane derivatives of the Formula I as claimed in claim 1 ##STR11## in which R¹ to R⁴, A and x have the meaning as in Formula I in claim 1, by reacting isocyanates with organic hydroxyl compounds, which process comprises reacting isocyanates of the Formula II, ##STR12## in which R¹ to R³ and A have the meaning as in Formula I, with equimolar amounts of hydroxyl compounds of the Formula III,

4. The process as claimed in claim 3, wherein the reaction is carried out in bulk or in inert organic solvents or in ethylenically unsaturated monomers capable of copolymerization which behave inertly under the reaction conditions, in the absence of water.

5. A process for the preparation of an ethylenically unsaturated, fluorine containing urethane derivative comprising reacting an isocyanate of the formula ##STR13## wherein R₁, R₂ and R₃ are individually selected from the group consisting of hydrogen and methyl and A is selected from the group consisting of --(CH₂)_y --, tertbutylphenylene, --C₆ H₄ --C(CH₃)₂ -- and --(CH₂)_b --(CO)_m --(Z--CH₂ CHR⁵)_n --(O--CO--NH--B)_p --, y is 1 to 6,b, m and p are 0 to 1, n is 1 to 5, Z is --O-- or --NH--, R⁵ is --H, --CH₃, or --C₂ H₅, and B is (C₆ to C₁₆) arylene optionally substituted with alkyl of 1 to 10 carbon atoms with an equimolar amount of an alcohol selected from the group consisting of 2,2,3,3-tetrafluoro-1-propanol, 1,1,1,3,3,3-hexafluoro-2-propanol, 2,2,3,4,4,4-hexafluoro-1-butanol, 2,3,3,4,4,5,5,5-octafluoro-1-pentanol, 2-perfluorohexylethanol and 2-perfluorooctylethanol.