Fluorochemical foam stabilizer and foamed polyurethanes made therewith

• US 4,356,273 A
• Filed: 12/22/1980
• Issued: 10/26/1982
• Est. Priority Date: 04/30/1979
• Status: Expired due to Term

• Current Assignee: Minnesota Mining and Manufacturing Co (3M Company)
• Original Assignee: Minnesota Mining and Manufacturing Co (3M Company)
• Inventors: Soch, Fredrich A.
• Primary Examiner(s): WELSH JR, MAURICE
• Application Number:
  US06/218,967
• Time in Patent Office: 673 Days
• Field of Search: 521/114, 521/115, 521/116, 521/164, 521/174
• US Class Current: 521/114
• CPC Class Codes: C08G 18/3861 containing sulfonamide and/or sulfonylhydrazide groups
• CPC Class Codes: C08G 65/00 Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
• CPC Class Codes: C08G 65/2639 the other compounds containing elements other than oxygen, nitrogen or sulfur
• CPC Class Codes: C08J 2375/04 Polyurethanes
• CPC Class Codes: C08J 2471/00 Characterised by the use of polyethers obtained by reactions forming an ether link in the main chain; Derivatives of such polymers
• CPC Class Codes: C08J 9/0061 characterized by the use of several polymeric components

Abstract

Active hydrogen-containing fluorochemical is used as a foam stabilizer in preparing polyurethane foams. For example, rigid or flexible polyurethane foams with high or low density and uniform cellular structure are prepared using fluoroaliphatic radical-substituted poly(oxyalkylene) polyols as foam stabilizers.

Claims

1. In a process for preparing a foamed polyurethane, the improvement comprising using a fluoroaliphatic radical-substituted poly(oxyalkylene)polyol as a foam stabilizer, wherein said stabilizer has the formula:

space="preserve" listing-type="equation">(R.sub.f).sub.m Q.sub.z [(RO).sub.x H.sub.y ].sub.n

where R_f is a fluorinated, saturated, aliphatic radical, R is a saturated aliphatic hydrocarbyl radical, H is an active hydrogen atom, Q is a linkage free of active hydrogen atoms and having a valence of m+n, m and n are integers of at least 1, z is an integer of 1-3, x is an integer of at least 25, y is an integer of at least 1, and the product ny is at least 2.

2. The process according to claim 1, wherein said stabilizer has a fluorine content of 4-25 weight percent.

3. The process according to claim 1, wherein said hydrocarbyl is ethylene and/or 2,3-propylene.

7. A foamed polyurethane made according to the process of claim 1.

4. In a process for preparing a foamed polyurethane, the improvement comprising using a fluoroaliphatic radical-substituted poly(oxyalkylene)polyol as a foam stabilizer, wherein said stabilizer has the formula:

##STR14## where R_f is a fluorinated, saturated, monovalent, aliphatic radical, Q is a linkage free of active hydrogen atoms and has a valence equal to m+n'"'"', m is an integer of at least 1, n'"'"' is an integer of at least 2, a and b are integers of at least 1, the sum of a+b being at least 5 and the weight ratio of a;

b being 20;

80 to 80;

20, said stabilizer having a fluorine content of 4-25 weight percent and an average molecular weight of at least 4500, and z is an integer of 1-3.

8. The process according to claim 4, wherein R_f is also stable, non-polar, inert, oleophobic, and hydrophobic, has 4 to 20 carbon atoms, and 40 to 78 weight percent fluorine and terminating in at least three fully fluorinated carbon atoms.

9. The process according to claim 8, wherein said R_f is straight chain, branched chain, cyclic, or a combination thereof and has a skeletal chain which can include catenary oxygen or trivalent nitrogen hetero atoms, or both said hetero atoms, bonded only to carbon atoms, and said Q is a valance bond or a polyvalent aliphatic, polyvalent aromatic, oxy, thio, carbonyl, sulfone, sulfoxy, --N(C₂ H₅)--, oxyalkylene, sulfonamido, carbonamido, sulfonamidoalkylene, carbonamidoalkylene, urethane, or urea radical.

10. The process according to claim 9, wherein R_f is perfluoroalkyl.

5. In a process for preparing a foamed polyurethane, the improvement comprising using a fluoroaliphatic radical-substituted poly(oxyalkylene)polyol as a foam stabilizer, wherein said stabilizer has the formula:

##STR15## where R_f is a fluorinated, saturated, monovalent, aliphatic radical, Q is a linkage free of active hydrogen atoms and having a valence equal to m+n'"'"', m is an integer of at least 1, n'"'"' is an integer of at least 2, and a and b are integers of at least 4 and designate blocks of oxyethylene and oxypropylene units respectively with the weight ratio of a;

b being 20;

80 to 80;

20, said stabilizer having a fluorine content of 4-25 weight percent an an average molecular weight of at least 4500, and z is an integer of 1-3.

11. The process according to claim 5, wherein R_f is also stable, non-polar, inert, oleophobic, and hydrophobic, has 4 to 20 carbon atoms, and 40 to 78 weight percent fluorine terminating in at least three fully fluorinated carbon atoms.

12. The process according to claim 11 wherein said R_f is straight chain, branched chain, cyclic, or a combination thereof and has a skeletal chain which can include catenary oxygen or trivalent nitrogen hetero atoms, or both said hetero atoms, bonded only to carbon atoms, and said Q is a valence bond or a polyvalent aliphatic, polyvalent aromatic, oxy, thio, carbonyl, sulfone, sulfoxy, --N(C₂ H₅)--, oxyalkylene, sulfonamido, carbonamido, sulfonamidoalkylene, carbonamidoalkylene, urethane, or urea radical.

13. The process according to claim 12 wherein R_f is perfluoroalkyl.

6. In a process for preparing a foamed polyurethane, the improvement comprising using a fluoroaliphatic radical-substituted poly(oxyalkylene)polyol as a foam stabilizer, wherein said stabilizer comprises:

##STR16## wherein a and b are integers of at least 4 and designate blocks of oxyethylene and oxypropylene units respectively, the ratio of oxyethylene units;

oxypropylene units being 20;

80 to 80;

20, said stabilizer having a fluorine content of 4 to 25 weight percent.